Heterobimetallic μ2-halocarbyne complexes

Liam K. Burt; Rian D. Dewhurst; Anthony F. Hill; Richard Y. Kong; Emily E. Nahon; Chee S. Onn

doi:10.1039/d2dt01558g

Heterobimetallic μ₂-halocarbyne complexes

Liam K. Burt, Rian D. Dewhurst, Anthony F. Hill, Richard Y. Kong, Emily E. Nahon, Chee S. Onn

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

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Abstract

The halocarbyne complexes [M(CX)(CO)₂(Tp*)] (M = Mo, W; X = Cl, Br; Tp* = hydrotris(dimethylpyrazolyl)borate) react with [AuCl(SMe₂)], [Pt(η²-H₂C CH₂)(PPh₃)₂] or [Pt(η²-nbe)₃] (nbe = norbornene) to furnish rare examples of μ₂-halocarbyne complexes [MAu(μ₂-CX)Cl(CO)₂(Tp*)], [MPt(μ₂-CCl)(CO)₂(PPh₃)₂(Tp*)] and [W₂Pt(μ₂-CCl)₂(CO)₄(Tp*)₂]. The complex [WPt(μ₂-CCl)(CO)₂(PPh₃)₂(Tp*)] spontaneously rearranges to the μ₂-carbido complex [WPt(μ₂-C)Cl(CO)₂(PPh₃)₂(Tp*)] during silica-gel chromatography. One phosphine ligand of [WPt(μ₂-CCl)(CO)₂(PPh₃)₂(Tp*)] is readily substituted by CO to afford [WPt(μ₂-CCl)(CO)₃(PPh₃)(Tp*)]. These μ₂-halocarbyne complexes have been interrogated by spectroscopic, crystallographic and computational methods, the latter by reference to data for terminal halocarbyne precursors [M( CX)(CO)₂(Tp*)].

Original language	English
Pages (from-to)	12080-12099
Number of pages	20
Journal	Dalton Transactions
Volume	51
Issue number	32
Early online date	22 Jun 2022
DOIs	https://doi.org/10.1039/d2dt01558g
Publication status	Published - 28 Aug 2022

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@article{1851e4ac96df434d920e6688fbbce5fa,

title = "Heterobimetallic μ2-halocarbyne complexes",

abstract = "The halocarbyne complexes [M(CX)(CO)2(Tp*)] (M = Mo, W; X = Cl, Br; Tp* = hydrotris(dimethylpyrazolyl)borate) react with [AuCl(SMe2)], [Pt(η2-H2C CH2)(PPh3)2] or [Pt(η2-nbe)3] (nbe = norbornene) to furnish rare examples of μ2-halocarbyne complexes [MAu(μ2-CX)Cl(CO)2(Tp*)], [MPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] and [W2Pt(μ2-CCl)2(CO)4(Tp*)2]. The complex [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] spontaneously rearranges to the μ2-carbido complex [WPt(μ2-C)Cl(CO)2(PPh3)2(Tp*)] during silica-gel chromatography. One phosphine ligand of [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] is readily substituted by CO to afford [WPt(μ2-CCl)(CO)3(PPh3)(Tp*)]. These μ2-halocarbyne complexes have been interrogated by spectroscopic, crystallographic and computational methods, the latter by reference to data for terminal halocarbyne precursors [M( CX)(CO)2(Tp*)].",

keywords = "Polynuclear metal-complexes, Ray crystal-structure, Carbyne ligands, Bridging carbene, Di-metal, Substituted acylphosphanes, Alkylidyne complexes, Tp-asterisk, Coordination chemistry, Aminocarbyne complexes",

author = "Burt, {Liam K.} and Dewhurst, {Rian D.} and Hill, {Anthony F.} and Kong, {Richard Y.} and Nahon, {Emily E.} and Onn, {Chee S.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = aug,

day = "28",

doi = "10.1039/d2dt01558g",

language = "English",

volume = "51",

pages = "12080--12099",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "32",

}

TY - JOUR

T1 - Heterobimetallic μ2-halocarbyne complexes

AU - Burt, Liam K.

AU - Dewhurst, Rian D.

AU - Hill, Anthony F.

AU - Kong, Richard Y.

AU - Nahon, Emily E.

AU - Onn, Chee S.

PY - 2022/8/28

Y1 - 2022/8/28

N2 - The halocarbyne complexes [M(CX)(CO)2(Tp*)] (M = Mo, W; X = Cl, Br; Tp* = hydrotris(dimethylpyrazolyl)borate) react with [AuCl(SMe2)], [Pt(η2-H2C CH2)(PPh3)2] or [Pt(η2-nbe)3] (nbe = norbornene) to furnish rare examples of μ2-halocarbyne complexes [MAu(μ2-CX)Cl(CO)2(Tp*)], [MPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] and [W2Pt(μ2-CCl)2(CO)4(Tp*)2]. The complex [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] spontaneously rearranges to the μ2-carbido complex [WPt(μ2-C)Cl(CO)2(PPh3)2(Tp*)] during silica-gel chromatography. One phosphine ligand of [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] is readily substituted by CO to afford [WPt(μ2-CCl)(CO)3(PPh3)(Tp*)]. These μ2-halocarbyne complexes have been interrogated by spectroscopic, crystallographic and computational methods, the latter by reference to data for terminal halocarbyne precursors [M( CX)(CO)2(Tp*)].

AB - The halocarbyne complexes [M(CX)(CO)2(Tp*)] (M = Mo, W; X = Cl, Br; Tp* = hydrotris(dimethylpyrazolyl)borate) react with [AuCl(SMe2)], [Pt(η2-H2C CH2)(PPh3)2] or [Pt(η2-nbe)3] (nbe = norbornene) to furnish rare examples of μ2-halocarbyne complexes [MAu(μ2-CX)Cl(CO)2(Tp*)], [MPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] and [W2Pt(μ2-CCl)2(CO)4(Tp*)2]. The complex [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] spontaneously rearranges to the μ2-carbido complex [WPt(μ2-C)Cl(CO)2(PPh3)2(Tp*)] during silica-gel chromatography. One phosphine ligand of [WPt(μ2-CCl)(CO)2(PPh3)2(Tp*)] is readily substituted by CO to afford [WPt(μ2-CCl)(CO)3(PPh3)(Tp*)]. These μ2-halocarbyne complexes have been interrogated by spectroscopic, crystallographic and computational methods, the latter by reference to data for terminal halocarbyne precursors [M( CX)(CO)2(Tp*)].

KW - Polynuclear metal-complexes

KW - Ray crystal-structure

KW - Carbyne ligands

KW - Bridging carbene

KW - Di-metal

KW - Substituted acylphosphanes

KW - Alkylidyne complexes

KW - Tp-asterisk

KW - Coordination chemistry

KW - Aminocarbyne complexes

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UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:000830674300001&DestLinkType=FullRecord&DestApp=WOS_CPL

U2 - 10.1039/d2dt01558g

DO - 10.1039/d2dt01558g

M3 - Article

C2 - 35895297

SN - 1477-9226

VL - 51

SP - 12080

EP - 12099

JO - Dalton Transactions

JF - Dalton Transactions

IS - 32

ER -

Heterobimetallic μ₂-halocarbyne complexes

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