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The reaction of alkynylselenolatoalkylidynes [W(≡CSeC≡CR)(CO)2(Tp*)] (R = SiMe3, SiiPr3, Ph, p-tolyl, tBu, CPh3, SiPh3, GePh3; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [AuCl(L)] (L = tetrahydrothiophene, SMe2) readily furnishes heterobimetallic complexes [WAu(μ-CSeC≡CR)Cl(CO)2(Tp*)] where gold(i) chloride coordinates to the tungsten–carbon multiple bond. Alternatively, desilylation of the SiMe3 complex [W(≡CSeC≡CSiMe3)(CO)2(Tp*)] in the presence of gold phosphine complexes [AuCl(PR′3)] (R′ = Ph or Cy) furnishes the gold alkynyl derivatives, [W(≡CSeC≡CAuPR′3)(CO)2(Tp*)]. [ABSTRACT FROM AUTHOR]

The reactions of [W(≡CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeC≡CR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(≡CSeC≡CR)(CO)2(Tp*)]. Desilylation of the SiMe3 complex furnishes the parent [W(≡CSeC≡CH)(CO)2(Tp*)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(≡CSeC≡CEPh3)(CO)2(Tp*)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp*)(CO)2W≡CSeC≡CSiRR′C≡CSeC≡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(≡CSeC≡C)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes. [ABSTRACT FROM AUTHOR]