A convenient synthesis of [HB(HImMe)3](PF6)2 (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)3] pro-ligand upon deprotonation with nBuLi. Reaction with [W(≡CC6H4Me-4)(CO)2(pic)2(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}]. Interrogation of experimental and computational data for this compound allow a ranking of familiar tripodal and facially coordinating ligands according to steric (percentage buried volume) and electronic (νCO) properties. The reaction of [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}] with [AuCl(SMe2)] affords the heterobimetallic semi-bridging carbyne complex [WAu(μ-CC6H4Me-4)(CO)2(Cl){HB(ImMe)3}].
