text:
Journal of Organometallic Chemistry (v.692, #21)
Contents (v-xvi).
Editorial Board (IFC).
Insertion chemistry of the metal–carbon bond: A tribute to Gerhard Erker by Timothy H. Warren (xvii-xix).
How to synthesize a constrained geometry catalyst (CGC) – A survey by Jesus Cano; Klaus Kunz (4411-4423).
Since the early 1990s constrained geometry complexes of group 4 metals have been studied as catalysts in olefin polymerizations and are now of major industrial importance. This article describes the development of this structurally highly diverse catalyst family providing a concise overview on synthetic entries to these organometallic complexes.Since the discovery of titanium- and zirconium complexes with linked cyclopentadienyl amido ligands, this new polymerization catalyst class (constrained geometry catalysts "CGCs") has attracted the interest of many research groups in industry and academia. In order to improve or modify the catalytic and polymer properties, numerous changes in the environment of the catalyst have produced a huge family of CGCs. The aim of this contribution is to provide a concise overview on synthetic entries to these structurally highly diverse catalysts – an organometallic guide to CGCs.
Keywords: Constrained geometry catalysts; Cyclopentadienyl amido ligands; Titanium; Zirconium; Polymerization;
Reactivity of the metal–cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds by Ruiting Liu; Xigeng Zhou (4424-4435).
The focus of this review concerns the reactivity patterns of metal–cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds. The advances in metal–carbon(η5) insertion chemistry have demonstrated that the π-bonding character provides additional reaction opportunities which are not shown by metal–alkyl compounds and these differences are highlighted.The focus of this review concerns the reactivity patterns of metal–cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds. The advances in the metal–carbon(η5) insertion chemistry have demonstrated that the π-bonding character provides additional reaction opportunities which are not shown by metal–alkyl compounds and these differences are highlighted.
Keywords: Insertion; Coupling reaction; Organometallic complexes; Cyclopentadienyl; Indenyl; Fluorenyl; Cycloheptatrienyl;
On the insertion processes of unsaturated molecules into the Nb–X σ-bond of " Cp 2 ′ NbX " moieties (Cp′ = η5-C5H4SiMe3; X = H, C, P) by Antonio Antiñolo; Santiago García-Yuste; Antonio Otero; Elena Villaseñor (4436-4447).
The Nb–X σ-bond of the formally 16-electron moieties " Cp 2 ′ NbX " (Cp′ = η5-C5H4SiMe3; X = H, C, P) undergoes insertion processes of different types of unsaturated molecules, namely CO, CO2, isocyanates, isothiocyanates, isonitriles, olefins and activated alkynes.In this article, we have reviewed a series of insertion processes of different types of unsaturated reagents, namely carbon monoxide, carbon dioxide, isocyanates, isothiocyanates, isonitriles, alkenes and activated alkynes, in the Nb–X σ-bond, X = H, C and P, of " Cp 2 ′ NbX " moieties, Cp′ = η5-C5H4SiMe3.
Keywords: Niobocene; Insertion;
Synthesis and reactivity of di(silylamido)cyclopentadienyl titanium and zirconium complexes by Jesús Cano; María Sudupe; Pascual Royo (4448-4459).
A short account of our recent contributions to the synthesis and reactivity of doubly silylamido-bridged cyclopentadienyl titanium and zirconium chelates is presented with particular emphasis on the insertion reactions of isocyanides into their M–N and M–C bonds and the efficiency of their alkyl-free cationic species as ethene polymerization catalysts and their deactivation pathways.We present in this account the synthesis and recent developments of a new class of group 4 metal complexes with the tridentate di(silylamido)cyclopentadienyl ligand. These doubly silyl-bridged group 4 metal amido chelates are receiving increasing interest as they are efficient catalysts for ethene polymerization when activated with MAO despite generating 14-electron d0 cationic species free of the alkyl group required for the first insertion reaction in the polymerization process.
Keywords: Silylamido; Cyclopentadienyl; Titanium; Zirconium;
Edge-bridged half-open zirconocenes: Synthesis, characterization, and reaction with diphenylacetylene by Benjamin G. Harvey; Vichien Kulsomphob; Atta M. Arif; Richard D. Ernst (4460-4466).
The synthesis and characterization of the half-open zirconocene, Zr(C5H5)(c-C8H11)(PEt3) (c-C8H11 = cyclooctadienyl), is described. The compound shows shorter Zr–C distances for the cyclooctadienyl ligand, in accord with expectations of stronger Zr–C bonding relative to C5H5. This compound reacts with two equivalents of diphenylacetylene to yield a bicyclic coupling product.The synthesis and characterization of the new, 16 electron half-open zirconocenes, Zr(C5H5)(c-C8H11)(PR3) (R = Me, Et) are reported, together with a structural study of the PEt3 complex. As with other low valent half-open zirconocenes, the Zr–C distances are significantly shorter on average for the electronically open dienyl ligand than those for the C5H5 ligand, 2.343 vs. 2.512 Å. Reaction of either of these compounds with PhC2Ph led to the incorporation of two equivalents of the alkyne, resulting in a formally 14 electron complex with coordination from cyclopentadienyl, allyl, σ-alkyl, and σ-vinyl units.
Keywords: Pentadienyl; Coupling reaction; Zirconium complex;
High-nuclearity ruthenium carbonyl cluster chemistry. 8: Phosphine activation, CO insertion, and deruthenation at a phosphido cluster – X-ray structures of [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] and [ppn][Ru7(μ7-P)(μ-η2-OCPh)(μ-PPh2)(μ-CO)(CO)17] by Michael D. Randles; Anthony C. Willis; Marie P. Cifuentes; Mark G. Humphrey (4467-4472).
Reaction of [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] with triphenylphosphine proceeds by loss of one cluster core vertex, phosphine P–C cleavage, and CO insertion into the putative Ru–phenyl bond to afford [ppn][Ru7(μ7-P)(μ-η2-OCPh)(μ-PPh2)(μ-CO)(CO)17] in low yield.Reaction of the square antiprismatic cluster [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] [ppn = bis(triphenylphosphoranylidene)ammonium] with triphenylphosphine proceeds by loss of one cluster core vertex, phosphine P–C cleavage, and CO insertion into the putative Ru–phenyl bond to afford [ppn][Ru7(μ7-P)(μ-η2-OCPh)(μ-PPh2)(μ-CO)(CO)17] in low yield, the first heptaruthenium μ7-phosphido-ligated cluster.
Keywords: Crystal structure; Ruthenium; Phosphido; Interstitial; Cluster;
Hydrogen sensitivity – A systematic computational study of electronic effects by Peter H.M. Budzelaar; Betty B. Coussens; Nic Friederichs (4473-4480).
DFT studies for model polymerization catalysts indicate hydrogen sensitivity decreases with increasing electrophilicity (measured as NH3 complexation energy) of the metal centre.Hydrogen sensitivity, defined as the preference of a metal alkyl for hydrogenolysis over olefin insertion, was studied computationally (DFT) for a series of simple model catalysts, including some metallocenes and a few basic models of heterogeneous catalysts. As a measure of electrophilicity, we have used the complexation energy to the probe molecule ammonia. For isolated species in the gas phase, complexation energies appear to dominate the chemistry. Ethene complexes more strongly than hydrogen, and with increasing electrophilicity of the metal centre this difference grows; the hydrogen sensitivity decreases accordingly. This result seems to agree both in broad terms with the experimental lower hydrogen sensitivity of heterogeneous catalysts, and more specifically with the increased hydrogen sensitivity of highly alkylated or fused metallocenes. The opposite conclusion reached by Blom et al. [R. Blom, O. Swang, R.H. Heyn, Macromol. Chem. Phys. 203 (2002) 381] is due to the use of a very different measure of electrophilicity, rather than to different experimental data.
Keywords: Hydrogen sensitivity; Hydrogen response; Metallocenes; Electrophilicity; DFT;
Reactions of the titanium-carbide species CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3 by Todd W. Graham; Christopher Ong; Pingrong Wei; Douglas W. Stephan (4481-4485).
Reaction of CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3 with ClSnMe3 and MeO3SCF3 afford the species [CpTi(μ2-Cl)(μ2-NPi-Pr3)(μ4-C)(μ2-Cl)(AlMe)(AlMe2)2] 1 and [CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(μ2-O3SCF3)(AlMe)(AlMe2)2] 2, respectively.The reaction of CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3 with ClSnMe3 and MeO3SCF3 affords the species CpTi(μ2-Cl)(μ2-NPi-Pr3)(μ4-C)(μ2-Cl)(AlMe)(AlMe2)2 1 and CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(μ2-O3SCF3)(AlMe)(AlMe2)2 2, respectively. Both 1 and 2 have been structurally characterized.
Keywords: Carbide; Titanium; Aluminum; Crystal structure;
Synthesis and reactions of heterodinuclear organopalladium complex having an unsymmetrical PN ligand by Nobuyuki Komine; Susumu Tsutsuminai; Masafumi Hirano; Sanshiro Komiya (4486-4494).
Reactions of novel heterodinuclear organopalladium–cobalt complexes having an unsymmetrical PN ligand (Et2NC2H4PPh2-κ2 N,P)RPd–ML n (ML n = Co(CO)4; R = Me, Ph) with CO yield corresponding acyl complexes (Et2NC2H4PPh2-κ2 N,P)(RCO)Pd–Co(CO)4 (R = Me, Ph). Rate of CO insertion was significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et2NC2H4PPh2-κ2 N,P) and methylpalladium–cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-κ2 P,P′)MePd–Co(CO)4.Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et2NC2H4PPh2-κ2 N,P)RPd–ML n (ML n = Co(CO)4; R = Me (2a), Ph (2b), ML n = MoCp(CO)3; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et2NC2H4PPh2-κ2 N,P) (X = I, NO3) with Na+[ML n ]−. Reversible dissociation of the Pd–N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et2NC2H4PPh2-κ2 N,P)(RCO)Pd–Co(CO)4 (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et2NC2H4PPh2-κ2 N,P) (1a), and methylpalladium–cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-κ2 P,P′)MePd–Co(CO)4 (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N′,N′-tetramethylethylenediamine ligand.
Keywords: Heterodunuclear organopalladium complex; Unsymmetrical PN ligand; CO insertion;
Optically active rhodium complexes with indenyl-linked phosphane ligands by Angelino Doppiu; Ulli Englert; Vera Peters; Albrecht Salzer (4495-4505).
The complexation of (S)-[2-(4,7-dimethyl-3H-inden-1-yl)-1-phenylethyl]diphenylphosphane with [Rh(μ-Cl)(η2-CH2CH2)2]2 affords the two diastereomers (S,R pl )-Rh 3 and (S,S pl )-Rh 4 in a ratio that depends strongly on the solvent. The complexes undergo oxidative addition of CH3I with high diastereoselectivity.The optically active indenyl-linked phosphane ligands (S)-[2-(3H-inden-1-yl)-1-phenylethyl]diphenylphosphane (L 1 ) and (S)-[2-(4,7-dimethyl-3H-inden-1-yl)-1-phenyl-ethyl]diphenylphosphane (L 2 ) were synthesized in three steps from (R)-1-phenylethane-1,2-diol in excellent yields. Their lithium salts reacted with [Rh(μ-Cl)(η2-CH2CH2)2]2 at −78 °C in THF affording the planar chiral complexes (S,R pl + S pl )-[Rh(η5-indenyl-CH2CH(Ph)PPh2-kP)(η2-CH2CH2)] and (S,R pl + S pl )-[Rh(η5-4,7-dimethylindenyl-CH2CH(Ph)PPh2-kP)(η2-CH2CH2)] as 61:39 and 15:85 mixtures of diastereomers. The complexes were isolated in optically pure form by column chromatography. The stereochemical configuration of one of the diastereomers was determined by X-ray crystallography. The complexation of L 2 was studied in different solvents and with several Rh precursors and diastereomeric excesses up to 76% were achieved. The ability of the chiral ligands to control the stereochemistry at the metal center was tested by oxidative addition of methyl iodide. Diastereomeric excesses greater than 98% were observed.
Keywords: Rhodium; Constrained geometry ligands; P ligands; Chirality; Oxidative addition; X-ray diffraction;
Synthesis and characterization of iron and cobalt dichloride bearing 2-quinoxalinyl-6-iminopyridines and their catalytic behavior toward ethylene reactivity by Wen-Hua Sun; Peng Hao; Gang Li; Shu Zhang; Wenqing Wang; Jianjun Yi; Maliha Asma; Ning Tang (4506-4518).
The 2-quinoxalinyl-6-iminopyridines and their iron(II) and cobalt(II) complexes were synthesized and full characterized. The molecular structures of (E)-N-(1-(6-(quinoxalin-2-yl)pyridin-2-yl)ethylidene)benzenamine and their metal complexes indicates rotations of the quinoxalinyl and imino-groups of ligand backbone during coordination, which suggests that the ligands form sterically-favored coordination with the metal center with the distorted trigonal-bipyramidal geometry. Upon activation with MAO, all iron complexes showed good catalytic activity for ethylene reactivity; while their cobalt analogues gave moderate to good activity for ethylene reactivity in the presence of MMAO.The 1-(6-(quinoxalin-2-yl)pyridin-2-yl)ethanone was synthesized in order to prepare a series of N-(1-(6-(quinoxalin-2-yl)pyridine-2-yl)ethylidene)benzenamines (L1–L7), which provided new alternative N∧N∧N tridentate ligands coordinating with iron(II) and cobalt(II) dichloride to form complexes of general formula LFeCl2 (1–7) and LCoCl2 (8–14). All organic compounds were fully characterized by NMR, IR spectroscopic and elemental analysis along with and magnetic susceptibilities and metal complexes were examined by IR spectroscopic and elemental analysis, while their molecular structures (L1, L4, 1, 4, 10, 13) were confirmed by single crystal X-ray diffraction analysis. Upon activation with methylaluminoxane (MAO), all iron complexes gave good catalytic activities for ethylene reactivity (oligomerization and polymerization), while their cobalt analogues showed moderate activities toward ethylene oligomerization with modified methylaluminoxane (MMAO). Various reaction parameters were investigated for better catalytic activities, the higher activities were observed at elevated ethylene pressure. The iron and cobalt complexes with para-methyl substituents of aryl group linked on imino group showed highest activity.
Keywords: 2-Quinoxalinyl-6-iminopyridines; Iron and cobalt complex; Ethylene oligomerization; Ethylene polymerization;
Regiochemistry of propene insertion with group 4 polymerization catalysts from a theoretical perspective by Andrea Correa; Giovanni Talarico; Luigi Cavallo (4519-4527).
Steric and electronic effects in the regiochemistry of monomer insertion in propene polymerization promoted by various metallocene, CGC and octahedral group 4 metal catalysts has been investigated by using DFT methods.The regiochemistry of monomer insertion in propene polymerization promoted by group 4 metal catalysts has been investigated by using DFT methods. We calculated primary and secondary propene insertion on metallocenes, constrained geometry catalysts and post-metallocene systems analyzing the effects of ligand framework, growing chain and metal. Our study supports the concept that for metallocene-based catalysts the regiochemistry of propene is mainly originated by steric effects. Instead, for octahedral systems a delicate balance between steric and electronic effects is found. This allows to play with the electronic properties of the ligand framework to tune finely the regiochemistry of polymerization.
Keywords: Propene polymerization; Regiochemistry; DFT calculations;
Acylzirconocene chloride: Formation of carbocycles by palladium-catalyzed cascade reaction by Yuji Hanzawa; Yusuke Oka; Masaya Yabe (4528-4534).
Acylzirconocene chloride complex as an acyl group donor reacts with ω-carbonyl α,β-enones or with bis-enones to give carbocyclic compounds under 10 mol% Pd(OAc)2-catalyzed conditions, and each reaction was accelerated by the addition of a stoichiometric amount of Me2Zn.Acylzirconocene chloride complex as an acyl group donor reacts with ω-carbonyl α,β-enones or with bis-enones to give carbocyclic compounds under 10 mol% Pd(OAc)2-catalyzed conditions, and each reaction was accelerated by the addition of a stoichiometric amount of Me2Zn. The formation of the carbocycles from ω-carbonyl α,β-enones was considered to be a result of a series of reactions; (i) the formation of Pd(II)-intermediate by an electron transfer from the Pd(0)-catalyst to an α,β-enone function in an initial step, (ii) an acyl group transfer from the acylzirconocene complex to the Pd(II)-intermediate (transmetalation), (iii) the reductive elimination of Pd(0)-metal, and (iv) an intramolecular addition of metal enolate to ω-carbonyl group. On the other hand, the reaction of bis-enones with acylzirconocene chloride under the identical condition afforded reductive cyclization product, bicyclo[3.3.0] octane derivatives, in which acyl group from acylzirconocene complex was not incorporated.
Keywords: Acylzirconocene chloride; Palladium catalyst; Cascade reaction; Reductive cyclization;
Remarkable Lewis acid effects on polymerization of functionalized alkenes by metallocene and lithium ester enolates by Yalan Ning; Hongping Zhu; Eugene Y.-X. Chen (4535-4544).
Drastic Lewis acid effects on polymerization of functionalized alkenes mediated by metallocene and lithium ester enolates are observed as well as elucidated.Drastic effects of Lewis acids E(C6F5)3 (E = Al, B) on polymerization of functionalized alkenes such as methyl methacrylate (MMA) and N,N-dimethyl acrylamide (DMAA) mediated by metallocene and lithium ester enolates, Cp2Zr[OC(O i Pr)=CMe2]2 (1) and Me2C=C(O i Pr)OLi, are documented as well as elucidated. In the case of metallocene bis(ester enolate) 1, when combined with 2 equiv. of Al(C6F5)3, it effects highly active ion-pairing polymerization of MMA and DMAA; the living nature of this polymerization system allows for the synthesis of well-defined diblock and triblock copolymers of MMA with longer-chain alkyl methacrylates. In sharp contrast, the 1/2B(C6F5)3 combination exhibits low to negligible polymerization activity due to the formation of ineffective adduct Cp2Zr[OC(O i Pr)=CMe2]+[O=C(O i Pr)CMe2B(C6F5)3]− (2). Such a profound Al vs. B Lewis acid effect has also been observed for the lithium ester enolate; while the Me2C=C(O i Pr)OLi/2Al(C6F5)3 system is highly active for MMA polymerization, the seemingly analogous Me2C=C(O i Pr)OLi/2B(C6F5)3 system is inactive. Structure analyses of the resulting lithium enolaluminate and enolborate adducts, Li+[Me2C=C(O i Pr)OAl(C6F5)3]− (3) and Li+[Me2C=C(O i Pr)OB(C6F5)3]− (4), coupled with polymerization studies, show that the remarkable differences observed for Al vs. B are due to the inability of the lithium enolborate/borane pair to effect the bimolecular, activated-monomer anionic polymerization as does the lithium enolaluminate/alane pair.
Keywords: Metallocene catalysts; MMA polymerization; Anionic polymerization; Block copolymers; Enolaluminates; Enolborates;
Synthesis and characterization of half-sandwich iridium complexes containing 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene and ancillary ortho-carborane-1,2-dichalcogenolato ligands by Ying-Feng Han; Jia-Sheng Zhang; Yue-Jian Lin; Jie Dai; Guo-Xin Jin (4545-4550).
Binuclear half-sandwich dichalcogenolate carborane iridium complexes 5a and 5b, connected with 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene ligands, have been synthesized and characterized structurally.The binuclear half-sandwich iridium complexes {Cp∗IrCl2}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and {Cp∗Ir[E2C2(B10H10)]}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (E = S(5a), Se(5b)) were prepared from the reaction of [Cp∗IrCl(μ-Cl)]2 or the "pseudo-aromatic" half-sandwich iridium complex Cp∗Ir[E2C2(B10H10)] (E = S(4a), Se(4b)) with a tetrathiafulvalene (TTF) derivative 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (2) at room temperature. The complexes (3, 5a and 5b) have been fully characterized by IR and NMR spectroscopy, as well as elemental analysis. And the molecular structures of 2 and 5a were established through X-ray crystallography. It is interesting that infinite tunnels are created by repeating 'buckled bowl' molecules of 5a.
Keywords: Iridium; Half-sandwich complexes; Carborane; Tetrathiafulvalene; Molecular structures;
Computational study of methane functionalization by a multiply bonded, Ni-bis(phosphine) complex by Thomas R. Cundari; Aaron W. Pierpont; Sridhar Vaddadi (4551-4559).
Theoretical study of methane functionalization by a multiply bonded, Ni-bis(phosphine) complex: [2+2] vs [1+2] pathways.A computational chemistry study of nickel-catalyzed group transfer to methane is presented. Analysis of the reaction energetics implies a possible competition between two mechanisms for carbene transfer, while for nitrene transfer, the [1+2] pathway is predicted to be the preferred route. For phosphinidene transfer, a [2π + 2σ] mechanism is preferred. Regeneration of the active species via a group transfer reagent XE is highly exothermic. The calculations indicate that (P ∼ P)Ni=E complexes deserve consideration as plausible starting points in the search for improved hydrocarbon functionalization catalysts.A computational chemistry study of nickel-catalyzed group transfer to methane is presented. Two mechanisms were evaluated: a one-step mechanism involving [1+2] insertion of E into the C–H bond of methane, and a two-step [2π + 2σ] mechanism involving addition of the C–H bond of methane across the Ni=E bond to a square planar NiII intermediate, followed by C–E reductive elimination. Analysis of the energetics for the different mechanistic steps implies a possible competition between the two mechanisms for carbene transfer. For nitrene transfer, the [1+2] pathway is predicted to be the preferred route. Finally, for phosphinidene transfer, the [2π + 2σ] mechanism is calculated to be the preferred mechanism. The two mechanisms studied – [1+2] and [2π + 2σ] – entail exothermic individual reactions, coupled with reasonable enthalpic barriers. Furthermore, regeneration of the catalyst active species by reaction with a group transfer reagent XE is highly exothermic. The calculations thus indicate that (P ∼ P)Ni=E (P ∼ P denotes a chelating bis-phosphine ligand) deserve consideration as plausible starting points in the search for improved hydrocarbon functionalization catalysts.
Keywords: Nickel; Catalysis; Density functional theory; Methane activation; Multiply bonded complexes; Group transfer catalysis;
Chiral, bridged bis(imidazolin-2-ylidene) complexes of palladium by Sabine K. Schneider; Jürgen Schwarz; Guido D. Frey; Eberhardt Herdtweck; Wolfgang A. Herrmann (4560-4568).
A systematic study of chiral bis(imidazolin-2-ylidene)palladium(II) complexes is presented, bearing the chiral group on the ring nitrogens. A structural proof of the chiral palladium(II) complexes is represented by a X-ray diffraction study.Varieties of chiral, bridged bisimidazolium salts as well as the synthesis of palladium complexes of general formula [ bridge { NC(H)=C(H)N ( R ∗ ) C ¯ } 2 PdBr 2 ] with the corresponding chelating N-heterocyclic carbene ligands is reported. This is the first systematic study of chiral bis(imidazolin-2-ylidene)palladium(II) complexes bearing chiral groups on the endocyclic nitrogens. Structural proof of such a chiral palladium(II) complex is presented by way of an X-ray diffraction study of complex 3a.
Keywords: Chelating ligands; Chiral ligands; Bisimidazolium salts; Palladium;
Highly active/selective and adjustable zirconium polymerization catalysts stabilized by aminopyridinato ligands by Winfried P. Kretschmer; Bart Hessen; Awal Noor; Natalie M. Scott; Rhett Kempe (4569-4579).
Sterically very demanding aminopyridinato ligands stabilize thermally robust, highly active and selective zirconium ethylene polymerization catalysts. Small changes in the bulky ligand periphery can be used to fine tune the nature of the formed polymers and even "living" ethylene polymerization at elevated temperatures (50 °C) can be observed.This paper describes a substantial enhancement of the aminopyridinato ligand stabilized early transition metal chemistry by introducing the sterically very demanding 2,6-dialkylphenyl substituted aminopyridinato ligands derived from (2,6-diisopropylphenyl)-[6-(2,6-dimethylphenyl)-pyridin-2-yl]-amine (1a–H, ApH) and (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridin-2-yl]- amine (1b–H, Ap∗H). The corresponding bis aminopyridinato zirconium dichloro complexes, [Ap2ZrCl2] (3a) and [Ap2 ∗ZrCl2] (3b) and the dimethyl analogues, [Ap2ZrMe2] (4a) and [Ap2 ∗ZrMe2] (4b) (Me = methyl) were synthesized, using standard salt metathesis routes. Single-crystal X-ray diffraction was carried out for the dichloro derivatives. Both zirconium metal centers have a distorted octahedral environment with a cis-orientation of the chloride ligands in 3a and a closer to trans-arrangement in 3b. The dimethyl derivatives are proven to be highly active ethylene polymerization catalysts after activation with [R2N(Me)H][B(C6F5)4] (R = C16H33–C18H37). During attempted co-polymerizations of α-olefins (propylene) and ethylene high activity and selectivity for ethylene and nearly no co-monomer incorporation was observed. Increasing the steric bulk of the ligand going from (2,6-dimethylphenyl) to (2,4,6-triisopropylphenyl) substituted pyridines, switches the catalyst system from producing long chain α-olefins to polymerization of ethylene in a living fashion. In contrast to the dimethyl complexes only [Ap2 ∗ZrCl2] in the presence of MAO at elevated temperature gave decent polymerization activity. NMR investigations of the reaction of dichloro complexes with 25 equiv. of MAO or AlMe3 at room temperature revealed, that [Ap2ZrCl2] decomposes under ligand transfer to aluminum and formation of [ApAlMe2], while [Ap2 ∗ZrCl2] remains almost unreacted under the same conditions. The aminopyridinato dimethyl aluminum complexes, [ApAlMe2] (5a) and [Ap∗AlMe2] (5b) were synthesized independently and structurally characterized. The aluminum complexes 5a and b show no catalytic activity towards ethylene, when "activated" with[R2N(Me)H][B(C6F5)4].
Keywords: Aluminum; Aminopyridinato ligands; N-ligands; Olefin polymerization; Zirconium;
Influence of the para-substitution in bis(arylimino)pyridine iron complexes on the catalytic oligomerization and polymerization of ethylene by Christian Görl; Helmut G. Alt (4580-4592).
A series of nine iron complexes with halogen or alkynyl functionalized bis(arylimino)pyridine ligands was synthesized and characterized. After activation with methylalumoxane (MAO), these catalysts oligomerize or polymerize ethylene to give highly linear products. The influence of substituents in the para-position of the iminophenyl rings was investigated.A series of nine bis(arylimino)pyridine iron complexes containing halogen or alkynyl substituents in their ligand frameworks was synthesized and characterized. After activation with methylalumoxane (MAO), these catalysts oligomerize or polymerize ethylene to give highly linear products. The introduction of halogen or alkynyl substituents in the para-position of the iminophenyl rings has a great influence on the polymerization activities of the corresponding iron complexes.
Keywords: Bis(arylimino)pyridine iron complexes; Ethylene polymerization; Oligomerization; Polyethylene;
Carbohydrate-containing N-heterocyclic carbene complexes by Friederike Tewes; Andreas Schlecker; Klaus Harms; Frank Glorius (4593-4602).
Novel carbohydrate bearing imidazolium salts have been synthesized and used for the in situ generation of the corresponding N-heterocyclic carbenes 1. These compounds were successfully used as catalysts of the conjugate umpolung of cinnamaldehyde to form γ-butyrolactones. In addition, silver and palladium complexes of these N-heterocyclic carbenes were synthesized and structurally characterized.Novel carbohydrate bearing imidazolium salts have been synthesized and used for the in situ generation of the corresponding N-heterocyclic carbenes. These compounds were successfully used as catalysts of the conjugate umpolung of cinnamaldehyde to form γ-butyrolactones. In addition, silver and palladium complexes of these N-heterocyclic carbenes were synthesized and structurally characterized.
Keywords: N-Heterocyclic carbenes; Carbohydrates; Palladium complex; Silver complex; Catalysis;
Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations by Lewis M. Broomfield; Yann Sarazin; Joseph A. Wright; David L. Hughes; William Clegg; Ross W. Harrington; Manfred Bochmann (4603-4611).
Mixed-ligand titanium (iminopyrrolato)(salicylaldiminato) complexes activated with MAO are highly effective ethylene/propylene copolymerisation catalysts. Activities and comonomer incorporation significantly exceeds those of either (N–N)2Ti or (N–O)2Ti systems.Treatment of MCl3(OC6H3-2- t Bu-6-CH=NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN=CHC4H3N]−), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N–O)(N–N). The molecular structures of TiCl2(OC6H3-2- t Bu-6-CH=NC6F5)(C2H5N=CHC4H3N) (1c), TiCl2(OC6H3-2- t Bu-6-CH=NC6F5)(C6H11N=CHC4H3N) (1b) and ZrCl2(OC6H3-2- t Bu-6-CH=NC6F5)(C6H11N=CHC4H3N) (2b) show distorted octahedral geometries with trans-O−,N−/cis-Cl2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.
Keywords: Titanium; Zirconium; Ethene; Copolymerization; Salicylaldiminate; Iminopyrrolate;
Zirconocene-promoted coupling reaction of terminal acetylenes to geminal enediynes in the presence of p-chloranil by Chanjuan Xi; Yuanyuan Liu; Xiaoyu Yan; Chao Chen (4612-4617).
Zirconocene-promoted trimerization of terminal acetylenes to zirconoenediynes in the presence of p-chloranil. Moreover, the resulting zirconoenediynes could be transformed into a variety of geminal enediynes through coupling reaction with electrophiles.Reaction of alkynyllithium with zirconocene dichloride in the presence of quinones afforded zirconoenediynes in good yields. Treatment of the zirconoenediyne with p-chloranil in the presence of CuCl afforded 1,1,4,4-tetraethynyl-1,3-diene in good yield. In the presence of CuCl and/or Pd(PPh3)4, the zirconoenediynes could be transformed into various enediyne derivatives through coupling reaction with electrophiles.
Keywords: Coupling reactions; Alkynes; Zirconium; Quinones; Enediynes;
Synthesis of functionalized isoindolinones: Addition of in situ generated organoalanes to acyliminium ions by Joshua G. Pierce; David L. Waller; Peter Wipf (4618-4629).
Addition of in situ generated di- or trisubstituted alkenylalanes to N-acyliminium ions provides rapid access to functionalized isoindolinones. Subsequent ring closing metathesis leads to tricyclic products. These transformations proceed under mild conditions and allow for the convergent synthesis of biologically significant scaffolds from readily available starting materials.Addition of in situ generated di- or trisubstituted alkenylalanes to N-acyliminium ions provides rapid access to functionalized isoindolinones. Subsequent ring closing metathesis leads to tricyclic products. These transformations proceed under mild conditions and allow for the convergent synthesis of biologically significant scaffolds from readily available starting materials.Display Omitted
Keywords: Isoindolinone; Aluminum; Zirconium; Hydrozirconation; Carbometallation; N-Acyliminium ion;
Coordination compounds of N,N′-olefin functionalized imidazolin-2-ylidenes by Ekkehardt F. Hahn; Beate Heidrich; Alexander Hepp; Tania Pape (4630-4638).
Palladium and nickel complexes with imidazolin-2-ylidene ligands bearing N-olefin substituents have been prepared from Pd(OAc)2 or [Ni(NCCH3)6](BF4)2. X-ray diffraction studies revealed formation of cis or trans square-planar complexes. Bromine abstraction from monocarbene cyclopentadienyl nickel complexes gave the trigonal-pyramidal nickel(II) complexes featuring N-allyl double bond coordination. N-Heterocyclic carbene ligands (NHC) were metalated with Pd(OAc)2 or [Ni(CH3CN)6](BF4)2 by in situ deprotonation of imidazolium salts to give the N-olefin functionalized biscarbene complexes [MX2(NHC)2] 3–7 (3: M = Pd, X = Br, NHC = 1,3-di(3-butenyl)imidazolin-2-ylidene; 4: M = Pd, X = Br, NHC = 1,3-di(4-pentenyl)imidazolin-2-ylidene; 5: M = Pd, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 6: M = Ni, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 7: M = Ni, X = I, NHC = 1-methyl-3-allylimidazolin-2-ylidene). Molecular structure determinations for 4–7 revealed that square-planar complexes with cis (5) or trans (4, 6, 7) coordination geometry at the metal center had been obtained. Reaction of nickelocene with imidazolium bromides afforded the η5-cyclopentadienyl (η5-Cp) monocarbene nickel complexes [NiBr(η5-Cp)(NHC)] 8 and 9 (8: NHC = 1-methyl-3-allylimidazolin-2-ylidene; 9: NHC = 1,3-diallylimidazolin-2-ylidene). The bromine abstraction in complexes 8 and 9 with silver tetrafluoroborate gave complexes [NiBr(η5-Cp)(η3-NHC)] 10 and 11. The X-ray structure analysis of 10 and 11 showed a trigonal-pyramidal coordination geometry at the nickel(II) center and coordination of one N-allyl substituent.
Keywords: Carbene; N-Olefin substituent; Palladium(II); Nickel(II); Structure determination;
Theoretical investigation on the model active site for isotactic polypropylene in heterogeneous Ziegler–Natta catalyst: A density functional study by Jin Woo Lee; Won Ho Jo (4639-4646).
The reaction mechanism of the stereoselective insertion of propylene monomer into the model active site created by Ti2Cl7 adsorption on the (1 0 0) surface of MgCl2 has been investigated by using DFT calculations.The stereoselectivity of the model active site formed by the adsorption of Ti2Cl7 on the (1 0 0) surface of MgCl2 was investigated by density functional calculations. The analysis of energetics for successive propylene insertions into the model active site reveals that the insertion of propylene into the model active site is energetically more favorable when a growing chain and one chlorine atom (that makes the active site chiral) are on the opposite side rather than on the same side. From this result, it is realized that the model active site is highly stereoselective. It is also observed that the Cl atoms near the growing chain significantly affect the activation energy barrier through the interaction with the growing chain.
Keywords: Theoretical methods; Density functional theory; Ziegler–Natta catalyst; Isotactic polypropylene; Stereoselectivity;
The epimetallation and carbonation of carbonyl and imino derivatives: Epivanadation route to 2-amino and 2-hydroxy acids by John J. Eisch; Paul O. Fregene; John N. Gitua (4647-4653).
The feasibility of hydrocarboxylating carbonyl and imino derivatives by a two-step process of epimetallation and carbonation has been demonstrated with 9-fluorenone and 9-fluorenone anil. With LiVH2 as the epimetallating agent, the process yielded 75% of 9-hydroxy-9-fluorenecarboxylic acid and 65% of 9-(N-phenylamino)-9-fluorenecarboxylic acid. Epimetallating reagents of vanadium and titanium also show promise.The feasibility of hydrocarboxylating carbonyl and imino derivatives by the two-step process of epimetallation and carbonation has been demonstrated with the model substrates of 9-fluorenone and 9-fluorenone anil. With lithium vanadium dihydride as the epimetallating agent, such hydrocarboxylation has led to a 75% yield of 9-hydroxy-9-fluorenecarboxylic acid and a 65% yield of 9-(N-phenylamino)-9-fluorenecarboxylic acid, respectively. Some initial success in extending the scope of this reaction to other substrates, such as benzophenone, has been achieved by using other epimetallating agents, like the presumed LiV(CH3)2 and Ti(OPr i )2. A brief review of the processes and organic synthetic applications of epimetallation and transfer epimetallation of C–C π-bonds is offered as background.
Keywords: Hydrocarboxylation; Epimetallation of C=E bond (E = O, N–R); Carbonation; Lithium vanadium(I) dihydride; Presumed lithium dimethylvanadate(I);
Synthesis and structural characterization of [(C5H4)SiMe2(N-t-Bu)]Ti[(o-C6H4)C(Ph)=C(Ph)], generated via an alkyne-Ti benzyne coupling reaction by Shawn M. Nettles; Jeffrey L. Petersen (4654-4660).
The thermolysis of [(C5H4)SiMe2(N-t-Bu)]TiPh2 in the presence of diphenylacetylene proceeds at 80 °C in cyclohexane solution with the formation of the titanacyclic complex [(C5H4)SiMe2(N-t-Bu)]Ti[(o-C6H4)C(Ph)=C(Ph)], which has been characterized by NMR and X-ray crystallography.The thermolysis of [(C5H4)SiMe2(N-t-Bu)]TiPh2 in the presence of diphenylacetylene proceeds at 80 °C in cyclohexane solution with the sole formation of the titanacyclic complex [(C5H4)SiMe2(N-t-Bu)]Ti[(o-C6H4)C(Ph)=C(Ph)], which has been characterized by solution NMR measurements and X-ray crystallographic analysis. This reaction is accompanied by the elimination of benzene and presumably occurs via coupling of a titanium benzyne intermediate with diphenylacetylene. The two chemically inequivalent Ti–C bonds of 2.081(7) and 2.103(6) Å in [(C5H4)SiMe2(N-t-Bu)]Ti[(o-C6H4)C(Ph)=C(Ph)] reflect the increased electrophilicity of the d0 Ti(IV) center arising from the presence of the bifunctional ansa-cyclopentadienyldimethylsilylamido ligand.
Keywords: Ti-benzyne intermediate; Coupling reaction; Titanacyclic complex;
Ion pair symmetrization in metallocenium cations partnered with diborane derived borate counteranions by Lee D. Henderson; Warren E. Piers (4661-4668).
The thermodynamics of ion pair symmetrization in a series of metallocenium species generated from Cp 2 ″ ZrMe 2 ( Cp ″ = 1 , 2 - Me 2 C 5 H 3 ) were studied using a variety of dynamic NMR techniques.The thermodynamics of ion pair symmetrization in a series of metallocenium species generated from Cp 2 ″ ZrMe 2 ( Cp ″ = 1 , 2 - Me 2 C 5 H 3 ) were studied using a variety of solution dynamic techniques including line broadening, 2D-EXSY, and 1D-DPFGSE-NOE. Ion pairs were generated by methide abstraction using the corresponding trityl salts [1-A] to yield [ Cp 2 ″ ZrMe ] + [ A ] - (A = {C6F4-1,2-[B(C6F5)2]2(μ-O(C6F5))}−, 2-O(C 6 F 5 ); {C6F4-1,2-[B(C6F5)2]2(μ-OPh)}−, 2-OPh; {C6F4-1,2-[B(C6F5)2]2(μ-OMe)}−, 2-OMe; and [B(C6F5)4]−, 2-B(C 6 F 5 ) 4 ). The observed activation parameters were interpreted on the basis of a solvent-assisted mechanism of ion pair symmetrization.
Keywords: Metallocenes; Ion pair symmetrization; Weakly coordinating anions; Fluoroarylborates;
Exploring reactivity of a bis-sulfonium zirconocene-ate dimer: Synthesis of various zwitterionic phosphonium anionic zirconocene complexes by Esteban Ortega; Nadine Pirio; Philippe Richard; Philippe Meunier (4669-4674).
A new class of stable zwitterionic phosphonium anionic zirconocene complexes containing at least one group 16 atom directly bonded to zirconium was prepared from reactions of a bis-sulfonium zirconocene-ate dimer with methylpropiolate, benzaldehyde, carbon disulfide and more simply with elemental sulfur and heavier chalcogens.Formal [3+2] cycloaddition reactions between the bis-sulfonium zirconocene-ate dimer ▪1a and methylpropiolate, benzaldehyde and carbon disulfide afforded stable zwitterionic phosphonium zirconocene-ate complexes 2–4, respectively, with two orthocondensed five-membered heterocycles. X-ray crystal structure of 4 has been determined. Elemental chalcogens (S, Se, Te) gave rise also to a new variety of five-coordinate zirconium(IV) complexes (5–7) by a formal [3+1] cycloaddition reaction. In these bicyclic zirconates, sulfur is included in a five-membered ring while the second chalcogen is in a four-membered one.
Keywords: Zwitterionic complexes; Zirconocene-ate; Anionic zirconocene; Phosphonium; Sulfonium; Chalcogens;
Effect of ketimide ligand for ethylene polymerization and ethylene/norbornene copolymerization catalyzed by (cyclopentadienyl)(ketimide)titanium complexes–MAO catalyst systems: Structural analysis for Cp∗TiCl2(N=CPh2) by Kotohiro Nomura; Junji Yamada; Wei Wang; Jingyu Liu (4675-4682).
Effects of the ketimide substituents for ethylene polymerization and ethylene/norbornene (NBE) copolymerization by Cp′TiCl2(N=CR1R2) [Cp′ = Cp (1), Cp∗ (2); R1,R2 = t Bu, t Bu (a), t Bu,Ph (b), Ph,Ph (c)]–MAO catalysts were investigated, and the structure of 2c was determined by X-ray crystallography.Ligand effects on the catalytic activity [and norbornene (NBE) incorporation] for both ethylene polymerization and ethylene/NBE copolymerization using half-titanocenes (titanium half-sandwich complexes) containing ketimide ligand of type Cp′TiCl2[N=C(R1)R2] [Cp′ = Cp (1), C5Me5 (Cp∗, 2); R1,R2 = t Bu, t Bu (a), t Bu,Ph (b), Ph,Ph (c)]–methylaluminoxane (MAO) catalyst systems have been investigated. CpTiCl2[N=C( t Bu)Ph] (1b) CpTiCl2(N=CPh2) (1c), and Cp∗TiCl2(N=CPh2) (2c) were prepared and identified; the structure of Cp∗TiCl2(N=CPh2) (2c) was determined by X-ray crystallography. The catalytic activity for ethylene polymerization increased in the order: 1a > 1b > 1c, suggesting that an electronic nature of the ketimide ligand affects the activity. However, molecular weight distributions for resultant (co)polymers prepared by 1b,c and by 2c–MAO catalyst systems were bi- or multi-modal, suggesting that the ketimide substituent plays a key role in order for these (co)polymerizations to proceed with single catalytically-active species. CpTiCl2(N=C t Bu2) (1a) exhibited both remarkable catalytic activity and efficient NBE incorporation for ethylene/NBE copolymerization.
Keywords: Titanium; Polymerization; Homogeneous catalysis; Ethylene; Norbornene; Copolymerization;
Regio- and stereospecific syntheses and structural characterization of alkyl-substituted 1,3-diene complexes of cyclopentadienylzirconium amidinates of the general formula: (η5-C5Me5)Zr[N( i Pr)C(Me)N( i Pr)](σ2,π-C4H5R) (R = Me or Et) by Philip P. Fontaine; Albert Epshteyn; Peter Y. Zavalij; Lawrence R. Sita (4683-4689).
New synthetic methods have been developed that provide several derivatives of the titled family of compounds in regio- and stereospecific fashion and for which structural characterization support a Zr(IV) σ2,π-metallacyclopent-3-ene limiting resonance form.Alkylation of Cp∗Zr[N( i Pr)C(Me)N( i Pr)](Cl)2 (Cp∗ = η5-C5Me5) (4) with 2 equiv. of n-hexyllithium in diethylether at −30 °C provided Cp∗Zr[N( i Pr)C(Me)N( i Pr)](n-C6H13)2 (5) in excellent yield. In solution, 5 undergoes thermally induced loss of "C6H16" to provide a 35% isolated yield of the 1,3-hexadiene complex, Cp∗Zr[N( i Pr)C(Me)N( i Pr)](C4H5Et) (6), in regio- and diastereochemically pure form. Ligand substitution of the η2-styrene group in Cp∗Zr[η2-CH2CH(C6H5)][N( i Pr)C(Me)N( i Pr)] (3) was achieved using an excess of 2-methyl-1,3-butadiene (isoprene) in toluene at 25 °C to provide Cp∗Zr[N( i Pr)C(Me)N( i Pr)](isoprene) (7) in regio- and stereochemically pure form. In similar fashion, an excess of cis,trans-1,3-pentadiene was used to separately prepare the isomeric diene complex Cp∗Zr[N( i Pr)C(Me)N( i Pr)](1,3-pentadiene) (8), once again in regio- and stereospecific fashion. Detailed experimental investigations of the molecular and electronic structures of 6–8, as performed in solution by 1D and 2D NMR spectroscopy and in the solid state by single-crystal X-ray analysis, revealed that the best structural description for these compounds is that of the Zr(IV) σ2,π-metallacyclopent-3-ene limiting resonance form rather than as a Zr(II) η4-diene complex.
Keywords: Group 4 metals; Conjugated dienes; Regiospecific; Stereospecific; Olefin polymerization catalysts;
(+)-Neomenthyl- and (−)-phenylmenthyl-substituted cyclopentadienyl and indenyl yttrocenes as catalysts in asymmetric hydroamination/cyclization of aminoalkenes (AHA) by Daniela V. Vitanova; Frank Hampel; Kai C. Hultzsch (4690-4701).
The synthesis of chiral terpenoid-substituted yttrocene complexes, in particular the yttrium analogue of Erker's neomenthylindenyl zirconocene is reported. The application of these complexes in asymmetric hydroamination/cyclization of aminoalkenes was investigated.The chiral, terpenoid-substituted yttrocene [(η5-neomenthylCp)2Y{o-C6H4CH2NMe2}] (1) can be prepared via facile arene elimination starting from [Y(o-C6H4CH2NMe2)3]. Compound 1 retains a C 1-symmetric structure in solution on the NMR time scale, due to tight binding of the amine donor. The (−)-phenylmenthyl-substituted complexes [(η5-(−)-phenylmenthylCp)2Y(μ-Cl)2Li(OEt2)2] (5) and [(η5-(−)-phenylmenthylCp)2YN(SiMe3)2] (6) were prepared via salt metathesis. Reaction of YCl3 with the planar chiral (1-neomenthylindenyl)lithium predominantly produced a single, C 2-symmetric, racemic-like diastereomer. The X-ray crystal structure analysis confirmed that [(η5-(+)-NMInd)2Y(μ-Cl)2Li(Et2O)2] (7) represents the same p-S, p-S metallocene diastereomer and adopts a very similar conformation as observed by Erker in his zirconocene complexes. Complex 7 reacts with LiN(SiMe3)2 to form [(η5-(+)-NMInd)2YN(SiMe3)2] (8) with retention of configuration. Complexes 1, 6 and 8 showed moderate to good catalytic activity in asymmetric hydroamination/cyclizations of aminoalkenes, but enantioselectivities were limited to a maximum of 38% ee for the sterically most hindered catalyst 8. The indenyl complex 8 is prone to protolytic loss of an indenyl ligand at low (⩽0.5%) catalyst loading, if sterically undemanding aminoalkene substrates are applied.
Keywords: Asymmetric catalysis; Hydroamination; Yttrium; Metallocene complexes;
Half-sandwich dibenzyl complexes of scandium: Synthesis, structure, and styrene polymerization activity by Julia Hitzbleck; Klaus Beckerle; Jun Okuda (4702-4707).
Half-sandwich dibenzyl complexes of scandium have been synthesized, structurally characterized and tested as syndiospecific styrene polymerization catalysts upon cationization.Half-sandwich dibenzyl complexes of scandium have been prepared by stepwise treatment of scandium trichloride with lithium derivatives of silyl-functionalized tetramethylcyclopentadienes (C5Me4H)SiMe2R (R = Me, Ph) and benzyl magnesium chloride. The resulting complexes [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] and [Sc(η5-C5Me4SiMe2Ph)(CH2Ph)2(1,4-dioxane)] show structure related to that of the corresponding bis(trimethylsilylmethyl) compounds [Sc(η5-C5Me4SiMe2R)(CH2SiMe3)2(THF)]. The four-coordinate complexes display η1-coordinated benzyl ligands without significant interaction of the ipso-carbon of the phenyl moiety. Conversion of [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] into the cationic species by treatment with triphenylborane in THF led to the formation of a stable charge separated complex [Sc(η5-C5Me4SiMe3)(CH2Ph)(THF) x ][BPh3(CH2Ph)]. Benzyl cation formed using [Ph3C][B(C6F5)4] in toluene resulted in a moderately active syndiospecific styrene polymerization catalyst.
Keywords: Scandium; Benzyl complexes; Styrene polymerization; Metallocene catalysis;
Insertion vs. site epimerization with singly-bridged and doubly-bridged metallocene polymerization catalysts by Stephen A. Miller (4708-4716).
A statistical model has been employed to determine the unidirectional site epimerization probability, ε, during propylene polymerization with singly-bridged and doubly-bridged C 1-symmetric metallocenes activated with methylaluminoxane. Generally, the probability of site epimerization increased as follows: carbon singly-bridged catalysts < doubly-bridged catalysts < silicon singly-bridged catalysts.A statistical model has been employed to determine the unidirectional site epimerization probability, ε, during propylene polymerization with the following C 1-symmetric metallocene precatalysts activated with MAO (MAO = methylaluminoxane): doubly-bridged rac-(1,2-SiMe2)2{η5-C5H2-4-(CHMe(CMe3))}{η5-C5H-3,5-(CHMe2)2}ZrCl2 (1) and (1,2-SiMe2)2{η5-C5H2-4-(1R,2S,5R-menthyl)}{η5-C5H-3,5-(CHMe2)2}ZrCl2 (2); and singly-bridged Me2C(3-(2-adamantyl)-C5H3)(C13H8)ZrCl2 (3) and Me2Si(3-(2-adamantyl)-C5H3)(C13H8)ZrCl2 (4). For 1/MAO a steep tacticity dependence on monomer concentration was found, as ε increased from 0.114 to 0.909 as [C3H6] decreased from 12.5 M to 0.5 M; similarly, ε increased for 2/MAO from 0.177 to 0.709. For 3/MAO, ε was moderately responsive to an increase in polymerization temperature, as ε increased from 0.000 to 0.485 from T p = 0–90 °C ([C3H6] = 1.1 M). Similarly, ε increased for 4/MAO from 0.709 to 0.913 from T p = 0–40 °C; at higher temperatures, bidirectional site epimerization was implicated.
Keywords: Metallocene catalysts; Polypropylene; Tacticity; Stereochemical model; ansa-Metallocene; Doubly-bridged metallocene;
Synthesis and characterization of titanium alkyl, oxo, and diene complexes bearing a SiMe2-bridged phenoxy-cyclopentadienyl ligand and their catalytic performance for copolymerization of ethylene and 1-hexene by Hidenori Hanaoka; Takahiro Hino; Masaaki Nabika; Tetsuya Kohno; Kazunori Yanagi; Yoshiaki Oda; Akio Imai; Kazushi Mashima (4717-4724).
A series of titanium alkyl, oxo, and diene complexes bearing a SiMe2-bridged phenoxy-cyclopentadienyl ligand were synthesized and characterized, and their catalytic behavior for copolymerization of ethylene and 1-hexene was investigated. X-ray analysis of 1,4-diphenyl-1,3-butadiene complex revealed that the diene ligand coordinates in s-cis fashion to titanium with a prone orientation. Polymerization study revealed that the alkyl complexes and the diene complexes showed higher activities than the starting dichloride at 130 °C.A series of titanium complexes bearing a SiMe2-bridged phenoxy-cyclopentadienyl ligand were synthesized and characterized, and their catalytic behavior for copolymerization of ethylene and 1-hexene was investigated. Treatment of dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)-titanium dichloride (1) with appropriate nucleophiles afforded dimethoxy complex 2, dimethyl complex 3, and dibenzyl complex 4. Standing a toluene solution of 2 in air afforded a dinuclear μ-oxo complex 5 as a single isomer. 1,3-Diene complexes 6–8 were prepared by reaction of 1 with the corresponding 1,3-dienes in the presence of 2 equiv. of n-BuLi. X-ray analysis of 1,4-diphenyl-1,3-butadiene complex 6 revealed that the diene ligand coordinates to titanium in s-cis fashion with a prone orientation. The newly prepared titanium complexes were applied to copolymerization of ethylene and 1-hexene upon activation with Al i Bu3 and [C6H5NMe2H][B(C6F5)4]. It was found that the alkyl complexes 3–4 and the diene complexes 6–8 showed higher activities than 1 at elevated temperature.
Keywords: Titanium complex; Cyclopentadiene; Phenolate; Diene; Polymerization;
Polymorphism of a nickel polymerization catalyst by Alexander Zeller; Georg Eickerling; Eberhardt Herdtweck; Martin U. Schmidt; Thomas Strassner (4725-4730).
Polymorphism of a nickel(II)salicylaldiminato polymerization catalyst is reported, the two structures differ significantly in the coordination geometry of the central metal atom. Lattice energy calculations were used to analyze the different solid state structures.Two polymorphs of an highly active nickel(II) salicylaldiminato polymerization catalyst are reported, which to our knowledge represent the first examples of polymorphism of catalytically active polymerization catalysts. The two structures differ significantly in the coordination geometry of the central metal atom. Lattice energy calculations were used to analyze the different solid state structures.
Keywords: Homogeneous catalysis; Solid state structure; Polymorphism; Nickel; N,O-ligands;
Zirconium-catalyzed methylalumination of heterosubstituted arylethynes: Factors affecting the regio-, stereo-, and chemoselectivities by Guangwei Wang; Gangguo Zhu; Ei-ichi Negishi (4731-4736).
The Zr-catalyzed methylalumination of heterosubstituted arylethynes containing O, S, Cl, and Si can proceed in high yields (>70%) and in a highly regio- and stereoselective manner (⩾98–99%), although SO2Ph, Br, and Cl in a benzylic position present serious chemoselectivity-related problems. The low regioselectivity of 60% initially observed with o-ethynylphenol (1a) has been elevated to ⩾98% through the use of either a catalytic amount of Zr(ebi)Cl2 or Zr(2-Me-Ind)2Cl2 or, more conveniently, the stoichiometric amount of ZrCp2Cl2, ZrCp2MeCl, or ZrCp2Me2 in conjunction with the use of a deficient amount (0.9 molar equiv.) of I2.The Zr-catalyzed methylalumination of heterosubstituted arylethynes containing O, S, Cl, and Si can proceed in high yields (>70%) and in a highly regio- and stereoselective manner (⩾98–99%), although SO2Ph, Br, and Cl in a benzylic position present serious chemoselectivity-related problems. The low regioselectivity of 60% initially observed with o-ethynylphenol (1a) has been elevated to ⩾98% through the use of either a catalytic amount of Zr(ebi)Cl2 or Zr(2-Me-Ind)2Cl2 or, more conveniently, the stoichiometric amount of ZrCp2Cl2, ZrCp2MeCl, or ZrCp2Me2 in conjunction with the use of a deficient amount (0.9 molar equiv.) of I2 for subsequent iodinolysis.
Keywords: Methylalumination with Me3Al; Heterosubstituted arylethynes; (E)-1-iodo-2-arylpropenes; ZrCp2Cl2 and its derivatives; Regio- and stereoselectivities;
Telomerization and dimerization of isoprene by in situ generated palladium–carbene catalysts by Ralf Jackstell; Anne Grotevendt; Dirk Michalik; Larbi El Firdoussi; Matthias Beller (4737-4744).
The palladium-catalyzed telomerization of isoprene with methanol and dimerization of isoprene has been studied in presence of palladium and imidazolium salts, which form in situ carbene ligands. A selectivity switch from the telomerization to the dimerization product occurred by using different substituted ligands.The palladium-catalyzed telomerization of isoprene with methanol and dimerization of isoprene have been studied in presence of in situ generated palladium–carbene catalysts. Unprecedented catalyst productivity has been observed for these two reactions. A selectivity switch from the telomer to the dimer product occurred by using different substituted carbene ligands. Among the imidazolium salts tested 1,3-dimesitylimidazolium mesylate (1), 1,3-dimesityl-4,5-dihydroimidazolium chloride (3) gave the best yields for telomerization reaction whereas 1,3-bis-(2,6-diisopropylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (5) and 1,3-bis-(2,6-diisopropylphenyl)-4,5-dimethyl-4,5-dihydroimidazolium chloride (9) form dimers in high yield and good selectivity.
Keywords: Carbenes; Dimerization; Homogeneous catalysis; Isoprene; Palladium; Telomerization;
A zwitterionic nickel–olefin initiator for the preparation of high molecular weight polyethylene by Yaofeng Chen; Brycelyn M. Boardman; Guang Wu; Guillermo C. Bazan (4745-4749).
Addition of 2 equiv. B(C6F5)3 to [3-(2,6-diisopropylphenylimino)-but-1-en-2-olato](η1-benzyl)(trimethylphosphine)nickel (1) results in the formation of 2-tris(pentafluorophenyl)borate-3-(2,6-diisopropylphenylimino)-but-1-ene(η3-benzyl)nickel (2), in which the borane coordinates to the oxygen of the ligand and forces binding of the olefin to nickel. Compound 2 can be used to initiate the homopolymerization of ethylene to obtain high molecular weight materials.The reaction of the sodium 3-(2,6-diisopropylphenylimino)-but-1-en-2-olato with Ni(PMe3)2(η1-CH2C6H5)Cl provides 3-(2,6-diisopropylphenylimino)-but-1-en-2-olato(η1-benzyl)(trimethylphosphine) nickel (1), which was structurally characterized. The addition of 2 equiv. of B(C6F5)3 to 1 results in the formation of 2-tris(pentafluorophenyl)borate-3-(2,6-diisopropylphenylimino)-but-1-ene(η3-benzyl)nickel (2), in which the borane coordinates to the O site of the ligand and forces binding of the olefin unit to the nickel center. The solid-state structure of 2 shows a zwitterionic structure with substantial positive charge at the nickel center. Compound 2 can be used to initiate the homopolymerization of ethylene to yield high molecular weight polyethylene.
Keywords: Homogeneous catalysis; Polyethylene; Nickel; Olefin complexes;
Cyclometalated group 4 complexes supported by tridentate pyridine-2-phenolate-6-(σ-aryl) ligands: Catalysts for ethylene polymerization and comparisons with fluorinated analogues by Ka-Ho Tam; Jerry C.Y. Lo; Zhengqing Guo; Michael C.W. Chan (4750-4759).
The pictured post-metallocene complexes (M = Ti, Zr, Hf) bearing the aromatic σ-carbanion as a chelating group have been prepared as olefin polymerization catalysts. The impact of different substituents on the σ-aryl moiety, especially at the R1 position, upon spectroscopic and polymerization characteristics have been examined.An adaptable synthetic methodology for the tridentate dianionic pyridine-2-phenolate-6-aryl [O,N,C] ligand framework, comprising the aromatic σ-carbanion moiety as a chelating component, has been developed. A series of non-fluorinated group 4 bis(benzyl) complexes supported by [O,N,C] auxiliaries, with halogen and alkyl groups at the 'R1' position ortho to the metal-C(σ-aryl) bond, have been prepared by exploiting the cyclometalation of the ligand. All derivatives have been characterized by NMR spectroscopy, and the spectral features concerning the metal-bound diastereotopic methylene groups have been highlighted. The capabilities of these complexes as catalysts for olefin polymerization have been tested, and comparisons with the recently reported fluorine-containing Ti-[O,N,C] analogues and related Hf-[N,N,C] derivatives are discussed. The titanium catalysts, in conjunction with MAO, displayed moderate to high activities for ethylene polymerization (up to 200 g mmol−1 h−1).
Keywords: Benzyl complexes; Cyclometalation; Olefin polymerization; Post-metallocenes; σ-Aryl ligand;
A unique coplanar multi-center bonding network in doubly acetylide-bridged binuclear zirconocene complexes: A density functional theory study by Shuqiang Niu; Agnes Derecskei-Kovacs; Michael B. Hall (4760-4767).
A unique π-conjugative six-center-six-electron bonding network was revealed in the doubly acetylide-bridged binuclear group 4 metallocene complexes. The coplanar multi-center bonding interaction between the metal centers and acetylide ligands not only significantly stabilizes the doubly acetylide-bridged complexes but also lowers the isomerization barrier.A unique π-conjugative interaction pattern was experimentally revealed in the doubly acetylide-bridged binuclear group 4 metallocene complexes, which was involved in C–C coupling/cleavage reactions of acetylides and σ-alkynyl migrations. To elucidate how this multi-center bonding network affects the structural and reaction properties of these complexes, density functional theory (DFT) calculations and molecular orbital (MO) analysis were carried out on the electronic structure and σ-alkynyl migration mechanisms of the doubly acetylide-bridged binuclear Zr complexes, (L2Zr)2(μ-CCH)2 (L = Cp, Cl). The B3LYP calculations suggested that the doubly [σ,π] acetylide-bridged complex C 2h -(L2Zr)2(μ-CCH)2 was produced by the reaction of L2Zr(CCH)2 with L2Zr through a C 2v -(L2Zr)2(μ-CCH)2 intermediate followed by an isomerization process. In particular, the isomerization of C 2h - or C 2v -(L2Zr)2(μ-CCH)2 is almost thermoneutral through a low barrier of 15.3–17.0 kcal/mol. The MO Walsh diagram revealed that the two isomers have a very similar six-center-six-electron bonding network. The coplanar π-conjunctive interaction by the electron donating and back-donating interactions between the metal centers and acetylide ligands significantly stabilizes the doubly acetylide-bridged binuclear group 4 metallocene complexes and the isomerization transition state.
Keywords: Density functional theory; C–C coupling; Coplanar multi-center bonding; Alkynyl migration mechanism; Isomerization transition state;
Enantioselective methylalumination of α-olefins by Robby A. Petros; James M. Camara; Jack R. Norton (4768-4773).
The ability of various enantiopure zirconocenes to catalyze the asymmetric methylalumination of allylbenzene has been tested. The enantioselectivity of an ethylene(Ind)2ZrCl2/MAO system is the same as that of authentic methyl cation generated with Ph3C+ from ethylene(Ind)2ZrMe2, confirming that the methyl cation is the active catalyst from ethylene(Ind)2ZrCl2/MAO.The ability of various enantiopure zirconocenes to catalyze the asymmetric methylalumination of allylbenzene has been tested. The enantioselectivity of an ethylene(Ind)2ZrCl2/MAO system is the same as that of authentic methyl cation generated with Ph3C+ from ethylene(Ind)2ZrMe2, confirming that the methyl cation is the active catalyst from ethylene(Ind)2ZrCl2/MAO.
Keywords: Ansa-metallocenes; Asymmetric carboalumination; Insertion;
Heterolytic CH-bond activation in the synthesis of Ni{(2-aryl-κC2)pyridine-κN}2 and derivatives by Emily C. Volpe; Andrew R. Chadeayne; Peter T. Wolczanski; Emil B. Lobkovsky (4774-4783).
When subjected to KO t Bu in Et2O, the bromides (2-aryl-pyridine)BrNi{(2-aryl-κC2)pyridine-κN} (aryl = phenyl, 2a; tolyl, 2b) generated the entitled bis-cyclometalated compounds, Ni{(2-aryl-κC2)pyridine-κN}2 (aryl = phenyl, 3a; tolyl, 3b), whose low spin configuration and rippled geometry were confirmed by X-ray crystallography and a DFT study.Thermolysis of Ni(OTf)2 in 2-phenyl-pyridine or 2-tolyl-pyridine afforded the cationic chelate derivatives, [bis(2-aryl-pyridine)Ni{(2-aryl-κC2)pyridine-κN}]OTf (aryl = phenyl, 1a; tolyl, 1b). Addition of KBr to 1a and LiBr to 1b provided the bromides, (2-aryl-pyridine)BrNi{(2-aryl-κC2)pyridine-κN} (aryl = phenyl, 2a; tolyl, 2b). When subjected to KO t Bu in Et2O, the bromides generated the entitled bis-cyclometalated compounds, Ni{(2-aryl-κC2)pyridine-κN}2 (aryl = phenyl, 3a; tolyl, 3b). These compounds insert diphenylacetylene into one cyclometalate arm to produce [(2-aryl-κC2)pyridine-κN]Ni[2-(2-(1,2-diphenylethenyl-κC2)aryl)pyridine-κN] (aryl = phenyl, 4a; p-tolyl, 4b). X-ray crystallographic studies were conducted on 1a, 2a, 3a and 4a, and a brief DFT study of 3a confirmed its low spin configuration and rippled geometry.
Keywords: Nickel; CH-bond activation; Alkyne; Insertion; Triflate; Cyclometalation;
Comparing propene polymerization with 1-butene polymerization catalyzed by MAO-activated C 2- and C 1-symmetric zirconocenes: An experimental and computational study on the influence of olefin size on stereoselectivity by Pierluigi Mercandelli; Angelo Sironi; Luigi Resconi; Isabella Camurati (4784-4791).
The propene and 1-butene polymerization behavior of a series of C 2- and C 1-symmetric zirconocenes has been reexamined. An attempt at rationalizing the observed influence of the olefin size on stereoselectivity on the basis of QM/MM calculations is reported.Polypropene and poly(1-butene) have been synthesized under very similar experimental conditions with a series of MAO-activated C 2-symmetric and C 1-symmetric ansa-zirconocenes. The C 1-symmetric zirconocenes bearing the bilaterally symmetric fluorenyl or bis(2-methylthieno)cyclopentadienyl ligand connected through a dimethylsilyl bridge to substituted indenyl ligands produce isotactic polybutene of similar or higher molecular mass and with noticeably higher isotacticity, compared to isotactic polypropene prepared with the same catalysts under comparable conditions. Structural and mechanistic reasons for such behavior are discussed on the basis of QM/MM calculations.
Keywords: Isotactic polypropylene; Isotactic polybutene; QM/MM calculations; 13C NMR; Metallocene catalysts; Stereoselective olefin polymerization;
Synthesis and characterization of heteroleptic iron(II) thiolate complexes with weak iron–arene interactions by Shun Ohta; Yasuhiro Ohki; Yohei Ikagawa; Rie Suizu; Kazuyuki Tatsumi (4792-4799).
Selective preparation of a series of heteroleptic thiolate complexes of iron(II) have been achieved using acid–base reactions of an iron–amide complex Fe{N(SiMe3)2}2 with various bulky thiols. All new complexes have been identified by X-ray crystallography. The iron center weakly interacts with the aromatic ring of thiolate ligands.Selective preparation and characterization of a series of heteroleptic thiolate complexes of iron(II) are described. The compounds were synthesized by treatment of iron bis-amide Fe{N(SiMe3)2}2 (1) with 1 equiv. of terphenyl thiols HS(2,6-(aryl)2C6H3) followed by addition of another equivalent of different thiol. An amide–thiolate intermediate [{(Me3Si)2N}Fe]2(μ-SDpp)2 (2; Dpp = 2,6-Ph2C6H3) was isolated from the 1:1 reaction of 1 and HSDpp. The X-ray crystal structures of all new thiolate complexes have been determined. The compounds crystallize as monomers or dimers, dependent on the substituents. They consist of distorted tetrahedral or trigonal-planar iron centers with weak interactions between the aromatic rings of thiolate ligands, where the Fe–C(arene) contact is 2.272(2) Å at shortest. The stronger iron–arene interaction appears to induce more pyramidalized geometry at the iron center.
Keywords: Iron; Thiolate; Heteroleptic complexes; Iron–arene interaction; Terphenyl group; Experimental methods;


text:
Featured Golf News
Longitudes & Latitudes Meshing at Chambers Bay
The gamble is paying off. Chambers Bay will be a terrific site for the 2015 U.S. Open.
I spent the day climbing over sand dunes in pursuit of the best views of the best players at the final day of stroke-play qualifying for this week's U.S. Amateur, which was being played for the first time on a public course, the first time on fescue grasses and for the first time on a layout measuring more than 7,700 yards.
As far as I could tell, the golf course in University Place, Wash., humbled players and delighted spectators, so firm and fast that it was at times too firm and fast, a links test true to the game's founding - if frustrated - fathers.
And all the while, so beautiful, the views of the water and mountains breathtaking and the course looking brown and slick like something on the edge of the Firth of Forth, not Puget Sound in the upper-left-hand corner of the U.S.
"I've never played anything like this," said Brian Higgins of Bellingham, Mass. "How do you explain how firm the course is without dropping a ball on cement and watching it bounce."
Added Eric Steger of Noblesville, Ind.: "I wish the Open were here next year so I could see how the pros attack it. It is so unlike anything I've ever played, and so much fun. It's not the same shots you normally hit. You have to be creative, try things you've never tried.
"When you're trying to qualify for the U.S. Amateur that isn't exactly comfortable, but it is awfully fun."
"It is pretty insane, but also pretty fun," intoned Nick Taylor, the star player at the nearby University of Washington and the country's most decorated collegiate golfer. "I've probably played it eight times before this month but it has never been like this. It is concrete with grass, but the same for everyone and a course that demands (that) you be creative.
"It will be an awesome match-play course this week. You have to hit two perfect shots to get a birdie putt. The reality is you can make a par and win a hole."
The color of the course is not to be confused with green or the lush grasses of a nearby park. "That grass is over-watered and over-fertilized," said Larry Gilhuly, the USGA's agronomist for the Western states, of the neighboring green belt. The new order of the USGA wants to spend less money and water maintaining golf courses. Chambers Bay is its new poster child.
Chambers Bay had never been as firm and reckless as Bandon Dunes in Oregon; nor as brown. Now it is. "We'll have it firm," promised Mike Davis of the USGA. "The fescue won't die when we turn the water off, it will just go dormant."
The USGA picked Chambers Bay to host the 2010 U.S. Amateur and 2015 U.S. Open eight months after the course's opening, an almost obscene gesture for such a storied old organization.
But their instincts are right. Here was a part of the country which had never hosted an Open, a place with splendid summer weather, no thunderstorms or natural causes to quell the excitement of a big golf tournament.
A place where the time zones work for network television on a site big and bold enough to house 70,000 fans a day, the most ever for an Open. A public place - within 20 minutes of SeaTac International Airport - along a working railroad line, up against blue waters dotted with small ferries and fishing boats, and within eyeshot of the jagged, snow-capped Olympic Mountains.
But will the golf course hold up? Locally, the big issue has been for it to survive limited public play and public criticism of a $20 million development that wasn't built to provide golf for locals, but to promote business and tourism.
So far, the course has had enough rounds (at $175 green fees - tops) to exceed operating expenses, but not enough to pay off all the debt incurred while building it.
When it opened, to the shock of Northwest golfers, the greens were slow and sandy; the whole place looked a little like what it had been: a sand and gravel pit. There was speculation the Open might be moved elsewhere because of the poor quality of the greens.
And with only one tree and massive fairways, would the course be tough enough for a U.S. Open? The slope from the back tees was only 135.
Well, the questions will be answered this week. Welcome to the world of links golf.
Surely, the course is suitably tough, as witnessed by the scores of the world's best amateurs; so far, less than a handful have broken par on Chambers Bay.
The greens are magnificent, rolling better than 11 on the Stimpmeter, easily fast enough for the dastardly slopes crafted by designer Robert Trent Jones II and his associates, Bruce Charlton and Jay Blasi.
Gilhuly says the course is just about perfect, the grass surrounding the greens as firm as the greens. He admitted there have been a few times when it was too firm, but added that was all part of the learning process for the U.S. Amateur, and eventually, the U.S. Open.
As far as the fans, the viewing is spectacular. Better than any major course I've ever seen. You can't see anything at St. Andrews. You can see everything here from the manufactured dunes that serve as perfect vantage points throughout the course.
On Tuesday, for the second straight day, more than 3,000 spectators were in attendance- much to the delight of the USGA. An official from the host committee said ticket sales and corporate sponsorships will cover the nearly $1 million Chambers Bay had to raise to pay for hosting the 2010 Amateur.
So far, the golf course is holding its own. "It is such a task to make a par out there, let alone a birdie," said Taylor, this year's Ben Hogan award winner who finished as the low amateur in last year's U.S. Open at Bethpage Black, another municipal course.
"It should be a great test for the Open.''
And the 2010 Amateur, too.
Blaine Newnham has covered golf for 50 years. He still cherishes the memory of following Ben Hogan for 18 holes during the first round of the 1966 U.S. Open at the Olympic Club in San Francisco. He worked then for the Oakland Tribune, where he covered the Oakland Raiders during the first three seasons of head coach John Madden. Blaine moved on to Eugene, Ore., in 1971 as sports editor and columnist, covering the 1972 Olympic Games in Munich. He covered five Olympics all together - Mexico City, Munich, Los Angeles, Seoul, and Athens - before retiring in early 2005 from the Seattle Times. He covered his first Masters in 1987 when Larry Mize chipped in to beat Greg Norman, and his last in 2005 when Tiger Woods chip dramatically teetered on the lip at No. 16 and rolled in. He saw Woods' four straight major wins in 2000 and 2001, and Payne Stewart's birdie putt to win the U.S. Open at Pinehurst. Blaine now plays golf at Wing Point Golf and Country Club on Bainbridge Island, Wash., where his current index is 12.6. In 2005, Blaine received the Northwest Golf Media Association's Distinguished Service Award. He and his wife, Joanna, live in Indianola, Wash., where the Dungeness crabs outnumber the people.
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text: From a domestic Plumbing and Heating business created in 1973, our company has evolved into the Mechanical and Electrical enterprise we are today. Our range of activities cover plumbing, heating, ventilation, electrical engineering, gas fitting, control systems, panel manufacturing, air conditioning, environmental control, renewable energy, low carbon systems, servicing & commissioning. Our engineers are qualified for gas, oil, electrical and refrigeration. The ultimate proof of good service is in the dedication and quality of the workmanship we provide.


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The new TRC 3 charger is backward compatible to charge Nickel-Cadmium and Nickel-Metal Hydride batteries as well as the new Lithium Ion.
Replacement battery charger. The TRC 3 charger is capable of charging Festool NiCD, NiMH and Lithium Ion batteries. It features intelligent monitoring electronics that protect the batteries from being overcharged or charged in hazardous conditions.
Note: This is the same charger that was included in the T 12+3 drill package (564247) & the T15+3 drill package (564250).
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Ever since I had basic Math prior to Algebra I in eighth grade, I have been fascinated by graphing. I think inherently it is becaue I am a visual person and when you graph information or numbers, it paints a truly vivid representation to you and THE NUMBERS JUMP OUT at you and their impact is unquestionable.
Within our blogging network of real estate professionals so many REALTORS do such a wonderful job with local market reports showing you trending on prices month after month, year over year, the amount of home inventory and even average days on market to sell a property. You will see graphs even on the percentage of distressed properties growing or declining in a certain town compared to a larger city nearby. All well and good and very relevant for each market area. REAL ESTATE IS LOCAL.
But my humorous self sees GRAPHS EVERYWHERE in life. Here is a sampling of late to perhaps let you appreciate and maybe SMILE just a little bit more in your day about how important all those numbers really are... it really is ALL ABOUT THE GRAPH. Enjoy and pass a smile on to another today will you???


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Ah, August. It is such a bittersweet month, isn't it? I mean, by mid-August, we're all gripping onto the last bit of summer break like that little round sticky thing suctioned on to the top of a mason jar - it's going to take a crowbar to pop us up off that sucker, right?
Most of us go unwillingly, kicking and screaming into the next season. It isn't because we don't appreciate the beauty of autumn it's just that, parting with summer is, you know, sad. How else can you describe losing up to five minutes of sunlight a day? And it only gets darker from here, my friends.
Anyway, that leaves me quite grateful for anything and everything that lengthens my favorite season.
Enter the phenomenon known as the garage sale.
Listen, I can't even believe I'm uttering the phrase aloud (well, OK, typing it out, to be more accurate). Because as soon as my mother and husband read this sentence, I'm toast. We're going to be hosting our umpteenth garage sale.
They like them. Me? No, thanks anyway.
Look, people, it isn't that I don't enjoy certain aspects of the whole ritual. I mean, I love the trip down memory lane as we sift through the stuff which we've not laid eyes upon since 1999. I'm thrilled to happen upon my favorite baby outfit of Kyle's (the one I bought for his Christmas pictures in 2000 and which I would not sell for even a million dollars, btw!) ... or my high school letterman's jacket ... or the coveted trophy I won in the sixth grade at the speech contest.
Ooh, I also love perusing through Kerry's baby pictures and Mom's Mom's teacups. Again, items with which I could not possibly be separated. Are you starting to see the problem?
I'm even OK with the three days' worth of work required to prepare for the sale. You know, the cleaning, the sorting, the pricing, the positioning.
Here's the portion of the process which I truly cannot stand ... the haggling.
This is the rub: I do not enjoy the whole bartering banter and I'm here to tell you right now that I will flat out give something away before I will get into a bidding war. I know. This defeats the whole objective. Getting the picture now?
"I know you have this marked as a dollar, but will you take a quarter?" is a typical garage sale inquiry.
"You must be joking. That's worth much more than a dollar to begin with," my husband usually jumps in and states. Because he knows.
He knows that I won't even bat an eyelash before I smile and tell the person inquiring to simply take the Thomas the Tank Engine disc.
"Patty, you can't just let people walk up and take this stuff," he and Mom will invariably protest. But I'm in agreement with my buddy and Liberty native Nancy Hastings' take on it.
"If I haven't used it in six months, let alone four years, I ain't missing it. Just take it away and save me the trouble of tossing it in the trash," is her overall philosophy.
I say let's just have a garage giveaway and get back to savoring whatever sunlight's left in August!
P.S.: Quick shout out to my niece Kelly and brother-in-law Kevin: Happy birthday to you both with much love!
Kimerer is a Tribune Chronicle columnist and garage sale grump. Contact her with your best offer on a first-edition WKBN Radio coffee mug at email@example.com.


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For my hair change at the end of May or beginning of June I'm going with a "theme".
It's very obvious.
Yes, Sir Frederic Leighton's Flaming June.
So strawberry blonde, and orange-red, and caramels... some touches of highlight.
Pary of me wants to throw some pink in there, but maybe I'll save those swaths of bright pink for after a couple of months of the theme hair.
This photo I saw inspired it... but I maybe want it brighter.


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It's a cold weather city. That automatically means its a good market!!!111
Actually, it isn't really, it's very rarely below freezing here.
I find this bizarre, though... there is absolutely no buzz about hockey here whatsoever, and word on the Sonics (who want a new building even though nobody here cares about them either, nor is there anything wrong with Key Arena) in the newspapers has been that they're going to relocate to [crappy suburb] Renton. This place is 100% Mariners and Seahawks all the time, even in the offseason. Nobody else rates.


text:
Dear people in Mapleprimes,
I calculated the following Quick Sort algorithm.
restart;quicksort:=proc(A::array(1,numeric),m::integer, n::integer) local partition, p;partition:=proc(m,n)i:=m;j:=n;x:=A[j];while i<j doif A[i]>x thenA[j]:=A[i];j:=j-1;A[i]:=A[j];elsei:=i+1;end if;end do;A[j]:=x;p:=j;end proc:if m<n thenp:=partition(m,n);quicksort(A,m,p-1);quicksort(A,p+1,n);end if;eval(A);end proc:
Then, in the answer, there was a sentence that
{--> enter , quicksort, , args = , a, , , 2, , , 2
{--> enter , quicksort, , args = , a, , , 4, , , 5
I could understand the reason of the "{--> enter , quicksort, , args = , a, , , 2, , , 2,"
but, I could not understand why 4, , , 5 could appear here. I think there is no reason why n that is the number at 5
increased from 2 to 5. I thought n continues to be 2.
I hope you will give me some hint for this understanding.
I thought it with a lot of time. And, I don't know whether this place is an appropriate place to ask this question.
But, I will be very glad if you teach me some of this.
Best wishes.
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Search for: cerita seks ngan anak dara
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Hula Hoops Deserve Better Than Rhythmic GymnasticsMagda Pecsenye
I was all over Facebook this morning complaining about how it's either horse dancing without the horses, or Knicks City Dancers without the basketball game. So then someone over at Buzzfeed decided to "prove" why it's actually awesome by showing us a bunch of photos of the rhythmic gymnasts doing things with hoops.
But here's the thing: My burlesque teacher (performance artist Howling Vic) was doing an act five years ago in which she did craaaazy things with a hula hoop to Nina Simone WHILE ALSO TAKING HER CLOTHES OFF. OVER HER HEAD.
So why is burlesque not an Olympic event if rhythmic gymnastics is?
I get that my own burlesque act (which was mostly my taking my clothes off while eating a bag of Cheetos, although there was more to it conceptually than just that, of course) is not Olympic-calibur (although Vic did invite me back to her farewell "all-stars" performance <blows on nails, buffs on shirt>).
But Vic should be in the Olympics, and should have the highest possible score for difficulty because of a) Nina Simone, b) taking a slip off over her head (no buttons or zipper to make things easy), and c) the hula hoop.
My point is this: There are women toiling away in obscurity doing amazing things with hula hoops all across this great country of ours who will never make it to the Olympics. Doesn't anyone feel for them? How can we celebrate rhythmic gymnastics when there are so many more excessive things that we could be doing with hula hoops? If we're really celebrating the human spirit, then we need to go higher, faster, stronger with hula hoops. It's our destiny.
Magda Pecsenye writes about parenting at AskMoxie.org and about co-parenting after divorce with her ex-husband at When The Flames Go Up.
Follow her on Twitter at @AskMoxie and join the AskMoxie Facebook page.
Follow her cat on Facebook at Alex the Assassin Cat.
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A Heartwarming Tale of Staggering Photoshop


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If you aspire to turn your brand into a household name, let's start by getting your name into current and potential customers' households. Whether you're presenting at a conference or participating at an event, make sure to send people home with promotional items and giveaways. Kitchen products and décor personalized with your logo are sure to receive repeated use and inspire brand recognition amongst renters and homeowners alike. Trigger recognition and bolster awareness with useful, customized gifts from ePromos.
Nylon Logo Tennis Balls are great for sports promotions and pets!
Quality rubber, huge imprints, attractive packaging and low prices make these Promo Jar Openers an excellent promotional value.
The Munch-it Clip Mouth Shaped Promotional Memo and bag clip closes bags to keep food fresh, and your logo visible.
This handy custom bag clip / memo clip will keep your logo visible at home or at the office.
You'll never get a piece of coal with your logo on this Custom Christmas Stocking.


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Welcome to the home of naked-photos.org To change this page, upload your website into the public_html directory Date Created: Tue Aug 20 09:20:37 2013
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Country Code: US
Country Name: United States
Region: California
City: San Diego
Latitude: 32.823811
Longitude: -117.197109
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|Web server
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[Querying whois.publicinterestregistry.net] [whois.publicinterestregistry.net] Domain Name:NAKED-PHOTOS.ORG Domain ID: D163613308-LROR Creation Date: 2011-10-16T12:43:41Z Updated Date: 2014-11-28T07:21:24Z Registry Expiry Date: 2015-10-16T12:43:41Z Sponsoring Registrar:eNom, Inc. (R39-LROR) Sponsoring Registrar IANA ID: 48 WHOIS Server: Referral URL: Domain Status: ok Registrant ID:d8978d42b2c1349b Registrant Name:WhoisGuard Protected Registrant Organization:WhoisGuard, Inc. Registrant Street: P.O. Box 0823-03411 Registrant City:Panama Registrant State/Province:Panama Registrant Postal Code:00000 Registrant Country:PA Registrant Phone:+507.8365503 Registrant Phone Ext: Registrant Fax: +51.17057182 Registrant Fax Ext: Registrant Email:firstname.lastname@example.com Admin ID:d8978d42b2c1349b Admin Name:WhoisGuard Protected Admin Organization:WhoisGuard, Inc. Admin Street: P.O. Box 0823-03411 Admin City:Panama Admin State/Province:Panama Admin Postal Code:00000 Admin Country:PA Admin Phone:+507.8365503 Admin Phone Ext: Admin Fax: +51.17057182 Admin Fax Ext: Admin Email:email@example.com Tech ID:d8978d42b2c1349b Tech Name:WhoisGuard Protected Tech Organization:WhoisGuard, Inc. Tech Street: P.O. Box 0823-03411 Tech City:Panama Tech State/Province:Panama Tech Postal Code:00000 Tech Country:PA Tech Phone:+507.8365503 Tech Phone Ext: Tech Fax: +51.17057182 Tech Fax Ext: Tech Email:email@example.com Name Server:NS1.AMERINOC.COM Name Server:NS2.AMERINOC.COM Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: Name Server: DNSSEC:Unsigned Access to Public Interest Registry WHOIS information is provided to assist persons in determining the contents of a domain name registration record in the Public Interest Registry registry database. The data in this record is provided by Public Interest Registry for informational purposes only, and Public Interest Registry does not guarantee its accuracy. This service is intended only for query-based access. You agree that you will use this data only for lawful purposes and that, under no circumstances will you use this data to(a) allow, enable, or otherwise support the transmission by e-mail, telephone, or facsimile of mass unsolicited, commercial advertising or solicitations to entities other than the data recipient's own existing customers; or (b) enable high volume, automated, electronic processes that send queries or data to the syt send queries or data stems of Registry Operator, a Registrar, or Afilias except as reasonably necessary to register domain names or modify existing registrations. All rights reserved. Public Interest Registry reserves the right to modify these terms at any time. By submitting this query, you agree to abide by this policy. gree to abide b


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German designer Werner Aisslinger has built a cabin covered in colourful Kvadrat textiles for the Danish brand's stand at this year's imm Cologne furniture fair (+ slideshow). More »
Tag: Werner Aisslinger
Bikini Island collection by Werner Aisslinger
for Moroso
Milan 2013: Berlin-based designer Werner Aisslinger will unveil brightly coloured chairs and a set of modular furniture for Italian brand Moroso in Milan next month (+ slideshow). More »
ADD System Furniture by Werner Aisslinger
for Flötotto
Product news: designer Werner Aisslinger of Berlin and Singapore has created a storage system for German brand Flötotto that's held together by plastic clips. More »
Dezeen Watch Store: Iconograph
chronograph by Werner Aisslinger
Dezeen Watch Store: new to Dezeen Watch Store this week is this chronograph addition to the Iconograph range by Berlin industrial designer Werner Aisslinger for Italian brand Lorenz. The watch is available to buy online or at our Dezeen Watch Store pop-up shop at Clerkenwell Design Week from 22 to 24 May. More »
Chair Farm by Werner Aisslinger
at Ventura Lambrate
Milan 2012: designer Werner Aisslinger of Berlin and Singapore will present a chair growing inside a greenhouse at Ventura Lambrate in Milan this week. More »
Iconograph by Werner Aisslinger in new colours
at Dezeen Watch Store
Dezeen Watch Store: the Iconograph watch by Berlin designer Werner Aisslinger is now available in four new colours at Dezeen Watch Store. More »
Iconograph by Werner Aisslinger for Lorenz
at Dezeen Watch Store
Dezeen Watch Store (and our pop-up store at 55 Neal Street until 16 July) is now stocking Iconograph, the first watch by Berlin designer Werner Aisslinger. More »
Fincube by Studio Aisslingera
Berlin designer Werner Aisslinger of Studio Aisslinger has completed a small mountainside mobile living unit in Ritten, Italy. More »
The Michelberger Hotel by Werner Aisslinger
Berlin designer Werner Aisslinger has completed a budget hotel designed to feel like staying at a friends house, which opens today in Berlin. More »
Coral by Studio Aisslinger
Milan 09: Berlin designers Studio Aisslinger present new work in Milan this week, including the Coral lamp shown above. More »
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ROCKFORD — The 2013 fall dean's list at Upper Iowa University includes more than a dozen local students.
Area residents who earned at least a 3.50 grade point average for the term include Amy Johns, Rockford; Brandon Schaffer, Rockford; Ellie Addotta, Winnebago; Eric Brown, Rockford; Dajana Djukic, Loves Park; Geneva Haley, Rockford; Fedja Harambasic, Rockford; Lorena Henao, South Beloit; Katharine Lupont, Rockford; Ryan Moore, Roscoe; Cela Ramirez, Rockford; Katie Stickler, Rockford; Lindsay Carroll, Roscoe.
For information: uiu.edu.
Location, ST | website.com


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State budget draws mixed reviews from local lawmakers
July 2, 2013
One House member feels the recently passed state budget is a good one, while another lashes out against the cuts it make with education. Overall, the 28.4 million spending plan represents a 2....
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The opening scene of "Life During Wartime" is a perfect representation of Todd Solondz's visual and thematic aesthetic.
Allen (Michael K. Williams) and Joy (Shirley Henderson) sit in a gaudily decorated restaurant booth. It's their wedding anniversary. Both are crying. He pours his heart out, thanking Joy for helping him through his myriad troubles. They're interrupted by their waitress, who recognizes Allen as the voice of a creepy, obscene serial prank caller, and is angered. They both plead that he has changed.
"We even threw out the phone book!" Joy implores.
As the moment unfolds, we laugh despite ourselves, squirm in our seats, feel the horror of shame, sense the poignancy of people in pain. This is Solondz pushing us outside of our comfort zones, forcing us to contemplate empathizing with unlikeable people, some of them self-confessed monsters. Are those who have caused others' suffering worthy of forgiveness, of happiness?
'Life During Wartime'
Rated: R for strong sexual content, brief nudity, and language including some disturbing dialogue
Cast: Allison Janney, Shirley Henderson, Ciaran Hinds, Dylan Riley Snyder
Director: Todd Solondz
Run time: 98 minutes
See it: Urban Institute for Contemporary Arts, 71 Sheldon Blvd. SE (454-7000, uica.org)
"Happiness" was, of course, the title of Solondz's infamous 1998 film, and "Wartime" revisits its characters and themes, with different actors cast in the roles. The writer/director's pointed, satirical, melodramatic tone is intact, but the setting has changed. Hence, the title, which suggests that the modern "war on terror" has deepened our anxieties and paranoia and made forgiveness an alien concept.
Twelve-year-old Timmy (Dylan Riley Snyder) is nearing his Bar Mitzvah. His room is decorated with war planes. He believes his father William (Ciaran Hinds) is dead, but his mother Trish (Allison Janney) has never told him the truth -- that her ex-husband is a convicted pedophile, just released from prison. Trish, meanwhile, finds love with another lonelyheart, Harvey Wiener (Michael Lerner), and gushes about how "normal" he is.
Joy and Trish are sisters. Joy, a sweetheart who works rehabilitating convicts, has regular conversations with the ghost of her former lover (Paul Reubens), who committed suicide. Meanwhile, William stalks his family, desiring information, but reluctant to upset them. His chance encounter with Jacqueline (Charlotte Rampling), a razor blade in a designer cocktail dress, is the film's most riveting, psychologically twisted moment, from a screenplay full of them.
Whether exploring explicitly taboo topics or prompting affected line readings from his cast, Solondz's intent is to provoke discomfort and discussion. Like its predecessor, "Life During Wartime" can be gloriously, exasperatingly, shockingly unsettling; you've been warned. We can forgive him for that, but we're not likely to forget his work.
E-mail John Serba: firstname.lastname@example.com and follow him on Twitter at twitter.com/johnserba


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On 2 Apr 2004 06:37:47 -0800, firstname.lastname@example.com (Uwe Kotyczka) wrote:
>I would like to use a tooltip in a way it was not designed for.
>When an end user clicks a certain checkbox in a dialog he shall
>see a warning "Are you sure...?".
>I'd prefer not using an anoying MessageBox but rather would do
>it by a tooltip. The tooltip should display immediately and at the
>checkbox position (even if it was checked by the keyboard).
>Can this be done easily? I tried to figure it out, but had no luck.
>Searching NGs didn't help me either.
You could place an ownerdraw button big enough to hold the text by the checkbox,
and when it's checked, use that.
i.e. Set flag, Invalidate button, Draw text, set timer, ontimer:clear flag,
invalidate button, draw blank.
Are you sure what you want to do is good design? (I'm not saying it isn't as I
don't know the app, but the user won't be able to answer the question.)