Fluoro-, Chloro-und Bromo-Wolfram(VI)-Alkinkomplexe. Die Kristallstrukturen von [K(18-Krone-6)l[WF5( P h -C = C -H ) | * CH3CN und | WCl4( P h -C = C -S e -/ i -C 4H 9)(C H 3CN)| 1991 Fluoro Petra Neumann K Urt Dehnicke Dieter Fenske G Erhard Baum Fachbereich Chemie Universität Marburg
Hans Meerwein-Straße D-3550 M arburg/Lahn
Institut für Anorganische Chemie Universität Karlsruhe
D-7500 Engesserstraße, Karlsruhe
Fluoro-, Chloro-und Bromo-Wolfram(VI)-Alkinkomplexe. Die Kristallstrukturen von [K(18-Krone-6)l[WF5( P h -C = C -H ) | * CH3CN und | WCl4( P h -C = C -S e -/ i -C 4H 9)(C H 3CN)|
Zeitschrift für Naturforschung B Z. Naturforsch. B 46 9 999 1010 1991 eingegangen am 4. Februar 1991
Tungsten Alkyne Complexes Synthesis IR Spectra 13C N M R Spectra Crystal Structure
Abstract

-, Chloro-, and Bromo-Tungsten(VI) Alkyne Complexes. The Crystal Structures of [K(18-Crown-6)][WF5(P h ~ C = C -H)] • C H 3CN and [WCl4(P h -C = C -S e -w -C 4 H9)(CH 3CN)] Several tungsten alkyne complexes o f the type [WC14(R -C = C -H) ] 2 and [WC14(R -C = C -R') ] 2 have been prepared by reactions o f WC16 with the alkynes in the presence o f C2C14. Treat­ ing with BrSiMe3 leads to corresponding bromo com plexes, whereas reactions o f N aF and KF, respectively, in acetonitrile solution in the presence o f crown ethers yield the fluoro complexes [N a(l 5-crown-5)][WFs(R -C = C -R ') ] and [K(18-crown-6)][W F5(R -C = C -R ') ] , respectively. All complexes were characterized by IR and l3C N M R spectroscopy. The crystal structures o f [K(18-crown-6)][W F5(P h -C = C -H) ] C H 3CN and [WCl4(P h -C = C -S e -« -C 4 H9)(C H 3C N)] have been determined by X-ray methods. [K(18-crown-6)][W F5(P h -C = C -H ] C H 3 CN: Space group P 2,, Z = 2, 8555 observed unique reflections, R = 0.034. Lattice dim ensions at -7 0 °C: a = 1199.4(3), b = 893.4(2), c = 1351.8(3) pm, ß = 109.73(3)°. The com pound forms ion pairs via three K -F contacts with bond lengths o f 262.0, 282.7, and 293.3 pm; the potassium ion is thus nine-fold coordinated by the six oxygen atoms o f the crown ether molecule and by three fluoride ligands. The alkyne ligand is bonded side on to the tungsten atom o f the [W F5(P h -C = C —H)] unit with WC bond lengths o f 202.4 and 202.6 pm, respectively. [WCl4(P h -C = C -S e -t t -C 4 H9)(C H 3C N)]: Space group P 2 Ja, Z = 4, 4595 observed unique reflections, R = 0.058. Lattice dim ensions at -7 0 °C: a = 1030.3(5), b = 1596.3(9), c = 1170.9(7) pm, ß = 104.28(3)°. The com pound has a molecular structure, in which the tungsten atom is seven-fold coordinated by four chloride ligands, by the two alkyne carbon atom s (WC bond lengths 200 and 203 pm), and in trans position to the latter by the nitrogen atom o f the acetonitrile molecule with a W -N bond length o f 226 pm.
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