TY - JOUR
T1 - Alkynylselenolatoalkylidynes (LnMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks
AU - Frogley, Benjamin J.
AU - Genet, Tobias L.
AU - Hill, Anthony F.
AU - Onn, Chee S.
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2019.
PY - 2019
Y1 - 2019
N2 - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)2(Tp∗)]. Desilylation of the SiMe3 complex furnishes the parent [W(CSeCCH)(CO)2(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh3)(CO)2(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)2WCSeCCSiRR′CCSeCW(CO)2(Tp∗)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp∗)(CO)2W(CSeCC)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.
AB - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)2(Tp∗)]. Desilylation of the SiMe3 complex furnishes the parent [W(CSeCCH)(CO)2(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh3)(CO)2(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)2WCSeCCSiRR′CCSeCW(CO)2(Tp∗)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp∗)(CO)2W(CSeCC)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.
UR - http://www.scopus.com/inward/record.url?scp=85066848701&partnerID=8YFLogxK
U2 - 10.1039/c9dt01504c
DO - 10.1039/c9dt01504c
M3 - Article
SN - 1477-9226
VL - 48
SP - 7632
EP - 7643
JO - Dalton Transactions
JF - Dalton Transactions
IS - 22
ER -