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Issue 13, 2017
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Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

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Abstract

The phosphinocarbyne complex [W([triple bond, length as m-dash]CPPh2)(CO)2(Tp*)] (1: Tp* = hydrotris(dimethylpyrazolyl)borate) coordinates transition metal fragments via the phosphine to form bimetallic species [W{[triple bond, length as m-dash]CPPh2RhCl2(Cp*)}(CO)2(Tp*)] (2) and [W([triple bond, length as m-dash]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{[triple bond, length as m-dash]CP([double bond, length as m-dash]S)Ph2}(CO)2(Tp*)], yielding [W{η2-C(AuCl)P([double bond, length as m-dash]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.

Graphical abstract: Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

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Publication details

The article was received on 19 Dec 2016, accepted on 01 Mar 2017, published on 02 Mar 2017 and first published online on 02 Mar 2017


Article type: Paper
DOI: 10.1039/C6DT04770J
Citation: Dalton Trans., 2017,46, 4355-4365
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    Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

    A. L. Colebatch and A. F. Hill, Dalton Trans., 2017, 46, 4355
    DOI: 10.1039/C6DT04770J

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