Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity†
a
and
Anthony F.
Hill
*a
Abstract
The phosphinocarbyne complex [W(![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
CPPh2)(CO)2(Tp*)] (1: Tp* = hydrotris(dimethylpyrazolyl)borate) coordinates transition metal fragments via the phosphine to form bimetallic species [W{CPPh2RhCl2(Cp*)}(CO)2(Tp*)] (2) and [W(CPPh2AuCl)(CO)2(Tp*)] (3). Appropriately tailored sterics allow for complexation of a second equivalent of AuCl to afford the trimetallic complex [W{η2-C(AuCl)PPh2AuCl}(CO)2(Tp*)] (4), containing an Au–W–C dimetallacyclopropene connectivity. Similarly, AuCl binds to the carbyne linkage in [W{CP(![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
S)Ph2}(CO)2(Tp*)], yielding [W{η2-C(AuCl)P(S)Ph2}(CO)2(Tp*)] (5). In the case of auration of the ditungsten species [W2(μ-C2PPh)(CO)4(Tp*)2] (6), variation in the stoichiometry leads to trimetallic [W2(μ-C2PPhAuCl)(CO)4(Tp*)2] (7) and pentametallic [W2{μ-(η2-CAuCl)2PPhAuCl}(CO)4(Tp*)2] (8) complexes, via a proposed tetrametallic intermediate [W2{μ-(η2-CAuCl)2PPh}(CO)4(Tp*)2], the site selectivity being dictated by aurophilic interactions.
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