Frogley, BenjaminGenet, TobiasHill, AnthonyOnn, Chee Sheng2020-07-07Dalton Trans., 2019, 48, 76321477-9226http://hdl.handle.net/1885/205883The reactions of [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeC[triple bond, length as m-dash]CR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W([triple bond, length as m-dash]CSeC[triple bond, length as m-dash]CR)(CO)2(Tp*)]. Desilylation of the SiMe3 complex furnishes the parent [W([triple bond, length as m-dash]CSeC[triple bond, length as m-dash]CH)(CO)2(Tp*)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W([triple bond, length as m-dash]CSeC[triple bond, length as m-dash]CEPh3)(CO)2(Tp*)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp*)(CO)2W[triple bond, length as m-dash]CSeC[triple bond, length as m-dash]CSiRR′C[triple bond, length as m-dash]CSeC[triple bond, length as m-dash]W(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([triple bond, length as m-dash]CSeC[triple bond, length as m-dash]C)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.We gratefully acknowledge the Australian Research Council (DP170102695 and DP130102598) for funding and the Australian National University of the award of a doctoral scholarship to CO.application/pdfen-AU© 2019 The Royal Society of Chemistry2019-04-2910.1039/c9dt01504c2020-05-17