Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

Annie L. Colebatch; Anthony F. Hill

doi:10.1039/c6dt04770j

Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

Annie L. Colebatch, Anthony F. Hill^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

33 Citations (Scopus)

Abstract

The phosphinocarbyne complex [W(≡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(=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.

Original language	English
Pages (from-to)	4355-4365
Number of pages	11
Journal	Dalton Transactions
Volume	46
Issue number	13
DOIs	https://doi.org/10.1039/c6dt04770j
Publication status	Published - 2017

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title = "Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity",

abstract = "The phosphinocarbyne complex [W(≡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(=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.",

author = "Colebatch, {Annie L.} and Hill, {Anthony F.}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c6dt04770j",

language = "English",

volume = "46",

pages = "4355--4365",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "13",

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T1 - Coordination chemistry of phosphinocarbynes

T2 - phosphorus vs. carbyne site selectivity

AU - Colebatch, Annie L.

AU - Hill, Anthony F.

N1 - Publisher Copyright: © The Royal Society of Chemistry.

PY - 2017

Y1 - 2017

N2 - The phosphinocarbyne complex [W(≡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(=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.

AB - The phosphinocarbyne complex [W(≡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(=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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U2 - 10.1039/c6dt04770j

DO - 10.1039/c6dt04770j

M3 - Article

SN - 1477-9226

VL - 46

SP - 4355

EP - 4365

JO - Dalton Transactions

JF - Dalton Transactions

IS - 13

ER -

Coordination chemistry of phosphinocarbynes: phosphorus vs. carbyne site selectivity

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