Han, Yong-ShenHill, AnthonyYuze Kong, Richard2020-12-112020-12-111359-7345http://hdl.handle.net/1885/216853The reaction of [W(CH)Br(CO)2(dcpe)] (dcpe = 1,2-bis(dicyclohexylphosphino)ethane) with tBuLi and SiCl4 affords the trichlorosilyl ligated neopentylidyne complex [W(CtBu)(SiCl3)(CO)2(dcpe)]. This slowly reacts with H2O to afford [W(CCH2 tBu)Cl3(dcpe)] and ultimately H2CCHtBu via an unprecedented alkylidyne homologation in which coordinated CO is the source of the additional carbon atom with potential relevance to the Fischer-Tropsch process.We gratefully acknowledge the Australian Research Council (DP170102695 and DP130102598) for fundingapplication/pdfen-AU© The Royal Society of Chemistry 2018201810.1039/c8cc00119g2020-11-23