trimethylenemethane complexelu

complexelu, languet-higgins mariyu argel parivartana-loha cyclobutadine complexela unikini anchanaa vaesaaru, dheenilo cyclobutadine yokka ksheeninchina kakshya saraina loham yokka dxz mariyu dies kakshyalato π paraspara charyaku saraina samaruupatanu kaligi untundi. eee sammelanam anchanaa vesina moodu samvatsaraala taruvaata samslaeshanha cheyabadindi mariyu idhi prayogaaniki mundu siddhaantam yokka andamaina kesugaa panichestundi. eee vijayavantamaina prayatnam itara sendriya ligandlanu kaligi unna kotta sammelanaala erpaatuku talupulu terustundi, ivi vaati swatantra sthithilo atyanta reactive anuvulu. aaa reactive anuvulannintilo, trimethylimethane (tmm) cyclobutadian complexela nundi atyanta sahajamaina utpannaanni kaligi undhi mariyu mariyu, emerson mariyu sahodyogulu modati trimethylimethane (tmm) transition metal complexes, (koo) (koo) 3phek (chii2) nivedinchaaru, idhi trimethylimethane complexela puraanaalaku prarambha binduvugaa maarindi. eee amsampai konni manchi sameekshalu eee amsaaniki marinta vanarulugaa upayogapadataayi.
trimethylenemethane complexela samslaeshanha.
saadhaaranamgaa cheppalante, trimethylenemethane complexelanu eee krindi naalugu margallo samslaeshanha cheyavachuhu (eah) α, α '-dihalosabstituted precursors yokka dehalogenation, (bii) η3-methyl complexela nundi xy (xy = hcl, br2, mariyu ch4) yokka thermal extrution, (sii) alcalydenecyclopropone yokka ring teravadam, mariyu (dii) functionalised allilsylanes (chitram 1) nundi nundi [x = oac, cl, os (o) 2me] tolagimpu.
α, α '-dehalosbustituted puurvagaamula dehalogenation.
trice (carbonyl)-η4-trimethylenemethehyrone (0) anedi samslaeshanha cheyabadina modati trimethylenemethane loha samudaayam mariyu idhi 3-chloro-2-chloromethylprop-1-een yokka yokka (koo) 9,] ledhaa ledhaa [phii (koo) 4] thoo praticharya nundi pondabadindi. eee phalitamgaa, aneka pratyaamnaaya trimethylenamethane inupa samudaayaalu triss (carbonyl)-η4-trimethylenamethane (0) tayaareeki upayoginche paddhatula maadirigaane tayaaru cheyabaddaayi.
η3-methyl complexela nundi ushna velikiteeta.
eee pratispandananu modata emerson nivedinchaaru.3-chloro-2-methylprope-1-een yokka yokka (koo) 9] thoo praticharya nundi pondina inupa allail complexes, inumu trimethylenemethane complexenu konugolu cheyadaaniki vaedi chesinappudu kullipotundi.
alcalydenecyclopropone yokka ring opening.
[fe2 (co) 9] samakshamlo, 2-pratyaamnaaya methylenecyclopropenal ring teravadam vividha kriyaatmaka samuuhaalanu kaligi unna vividha η4-trimethylenamethane complexela erpaatuku daariteestundi, (r1 = h, r2 = Ph), (r1 = naaku, r2 = Ph), (r1 = r2 = Ph), mariyu (r1 = h, r2 = ch = ch2). eee vyuuhamloo atyanta aasaktikaramaina bhaagam stereochemistry mariyu idhi stereosphaciphic deuterium labeling prayogaala dwara spashtam cheyabadindi. (chitram 3) 
functionalised allilsylanes nundi nundi [x = oac, cl, os (o) 2me] nuu tolaginchadam.
tolaginchadam six (x = oac) nuu tolaginchadaaniki mariyu atyanta reactive η3-trimethylenamethane palladiumnu utpatti cheyadaaniki [pd (pph3) 4] vadakanni modata troast mariyu chaan nivedinchaaru. taruvaata, oka oka loha kendramtho allilsailenla praticharya lohaniki aakseekarana adanamgaa dwara munduku saagutundani kanugonabadindi, phalitamgaa oka η1-allil complexes erpadutundi, taruvaata oka η3-allil complexes erpadutundi, chivaraku η4-trimethylenemethane complexes (chitram 4) nuu ivvadaaniki ivvadaaniki tolaginchabadutundi. pratipaadita intermidate yokka isolation eee yantraamgaanni marinta dhruveekarinchindi.
nirmaanam mariyu bandham.
nirmaanam yokka aakruti.
gyaas faze electron defraction upayoginchi chesina oka adhyayanamlo, triss (carbonyl)-η4-trimethylenemethane iron inumu kendram gurinchi asthiramaina aakrutini avalambistundani nirdhaarinchabadindi. carbonyl mariyu trigonal-pyramidal trimethylenemethane kaligi unna ligandlu, saadhaarana godugu-rakam aakruteekaranalo amarchabadi untaayi. trimethylenemethane ligand yokka kendra carbon bayati methylene carbonlatho poliste inumu kendraaniki daggaragaa untundi. idhi 1.94 (1) Â koliche phii-sii (central) dhooram dwara nirdhaarinchabadindi, ayithe phii-chii dhooraalu 2.12 Â vadda kolichabaddayi. eee phalitaalu chitram chitram pradarsinchabaddaayi. antekakunda, eee phalitam ex-rae vivartana mariyu kampana varnapatam dwara kooda nirdhaarinchabadindi.
bandhaala vislaeshanha.
chitram 6a loe samarpinchina kakshya paraspara charya rekhaachitram oka samathooka trimethylimethane ligand mariyu asthiramaina jyaamitiloo oka phe (koo) 3 sakalam madhya erpadina sanklishtamlo keelaka bandha paraspara charyanu vivaristundi. pratyaekamgaa, rekhaachitram praathamika bandha paraspara charya anedi trimethylenemethane ligandpai "2e" phe (koo) 3 sakalam mariyu "e" madhya sambhavistundani highlight chestundi. ayithe, loha-trimethylenemethane aksham 60° dwara grahana jyaamitiloki tippabadithe, "2e" mariyu "e" madhya paraspara charya taggutundi. eee taggimpu phalitamgaa sanklishtamlo homo yokka shakti perugutundi, idhi chitram 6b loe chuupina vidhamgaa bhramanaaniki addankini andinche mukhyamaina amsam.
podiginchina huckel gananalu planner trimethylenemethane ligaandnu upayoginchi 87 kj mol−1 yokka avarodhaanni istayi. prayogaatmaka jyaamitini pooli unde trimethylenemethane ligandku oka puckered conformation parichayam cheyadam, lekkinchina avarodhamlo 98.6 kj kj perugudalaku daariteestundi. eee pucking anedi s aksharanni "e" kakshyalaloki kalapadanni prerepistundi, idhi loha kendram vaipu marinta spashtamaina dhoranini kaligistundi. tatphalitamgaa, "e" mariyu "2e" kakshyala madhya ativyaapti merugupadutundi. θ dwara vargeekarinchabadina puckering yokka degree, 12° paridhiloo untundi. s" aksharanni "e" loki kalapadam valla kooda h-c-h vimanam lohaniki dhooramgaa untundi. c-1 mariyu c-2 mariyu vimanam h-c-h madhya konam β, saadhaaranamgaa 15° untundi.
η4-trimethylenemethane complexela praticharyalu.
aneka aasaktikaramaina lakshanaalanu kaligi unna oka manoharamaina sanklishtamgaa, trimethylenamethane complexelu eee krindi vaatitho praticharyalanu kaligi unnatlu kanugonabadindih (eah) electrophiles; (bii) nucleophiles; (sii) trutheeya phosphines; mariyu complexelu kooda (dii) redox praticharyalanu kaligi undavacchu.
electrophiles thoo praticharyalu.
manchi π vyavasthatho, iron trimethylenemethane complexelu electrophilic daadiki gurayye avakaasam undhi. trice (carbonyl)-η4-trimethylenemethane ironku hydrochloric aamlam jodinchadam valla chlorotris (carbonyl)-2-methylaliliron (ii) labhistundi. pratyaamnaaya trimethylenamethane inupa samudaayaalu, marovaipu, cross-conjugated dynyl inumu catayans mariyu η4-diane complexelanu utpatti cheyadaaniki balamaina aamlaalatoe pratispandistaayi.
nucleophilestho praticharyalu.
electronfiles thoo praticharyala maadirigaane, catanic malibdinum trimethylimethane complexes trimethylimethane ligand vadda nucleophilic daadiki gurayye avakaasam unnatlu kanugonabadindi. idhi tatastha η3-allil complexela erpaatuku daariteestundi.
trutheeya phosphinelatho praticharyalu.
catanic complexes [ir {η4-c (ch2) 3} (co) (pph3) 2] pf6 (complexes 1) gadhi ushnograta vadda vividha trutheeya phosphine ligandla patla vegavantamaina praticharyanu pradarsistundi. ethyldephenylphosphinic samaanamaina 1 moltho chikitsa chesinappudu, 1:1:1 mishrama samudaayaalu [ir {η4-sii (ch2) 3} (koo) (koo) 2] dippe] (sanklishta 2), [ir {η4-sii (ch2) 3} (koo) (koo) (pmef2) dippe] (sanklishta 3), mariyu [ir {η4-sii (ch2) 3} (koo) (koo) 2] dippe] (sanklishta 1) erpadutundi. sanklishta sanklishta methyldefenilphosphine yokka 2 molku samaanamaina padaarthaalanu jodinchadam valana sanklishta 2 adhika digubadini istundi. adevidhamgaa, complexes 1 1,2-bis (diphenylphosphino) eethaen (dippe) thoo pratispandinchi [ir {η4-sii (ch2) 3} (koo) dippe] dippe] nuu istundi. eee praticharyalu eee catanic iridium complexeloni phosphine ligandlu labyl anie pradarsistaayi. antekakunda, sanklishtamaina [ir {η4-c (ch2) 3} (co) 2 (pph3)] pf6 kuu methyldephenylphosphinic samaanamaina 1 molnu jodinchadam dwara carbonyl ligand sthaanabhramsham chendutundi, idhi 1,2 mariyu 3 sanklishtatala 1:1:1 misramaanni istundi.
redox praticharyalu.
ippati varaku, trimethylenemethane complexela yokka redox praticharyalu ippatikee parimitam. oka iconic udaaharana electron-ritch complexelu [phii {η4-c (ch2) 3 (l) 3] (l = pme ledhaa pme2ph) (complexes 4). sylver trifluoromethanesalphonate kuu samaanamaina 1 thoo aakseekarana taruvaata, tatastha trimethylenemethane complexelu 4 vaati sambandhita catanic 17-electron complexeluga roopaantaram chendutaayi. eee aakupaccha aakseekarana complexelu, sodiyam diethylmalonate ledhaa sodiyam borohydridetho praticharyala dwara vaati asalu tatastha trimethylenemethane roopaalaku tirigi punarutpatti cheyavachu (chitram 7).

