A [C1 + C2] route to propargylidyne complexes

Anthony F. Hill; Richard A. Manzano

doi:10.1039/c9dt00876d

A [C₁ + C₂] route to propargylidyne complexes

Anthony F. Hill^*, Richard A. Manzano

^*Corresponding author for this work

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

16 Citations (Scopus)

Abstract

The reactions of [W(CBr)(CO)₂(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with a range of terminal alkynes (RCCH), mediated by [Pd(PPh₃)₄] and CuI, afford new proparylidynes [W(C-CCR)(CO)₂(Tp∗)] [R = ^tBu, C₆H₄X (X = H, NH₂, NO₂), ferrocenyl, APh₃ (A = C, Si, Ge), B(O₂CCH₂)₂NMe]. Similar treatment of [W(CBr)(CO)₂(Tp∗)] with Ph₂Si(CCH)₂ affords the ditungstaoctatetrayne [W₂(μ-C₆)(CO)₄(Tp∗)₂] while the bimetallic complex [W₂{μ-(CCC)₂SiPh₂}(CO)₄(Tp∗)₂], which is obtained from [W(CBr)(CO)₂(Tp∗)] and Ph₂Si(CCSnPh₃)₂, reacts with [AuCl(THT)] (THT = tetrahydrothiophene) to provide the tetrametallic complex [W₂Au₂{μ-(CCC)₂SiPh₂}Cl₂(CO)₄(Tp∗)₂].

Original language	English
Pages (from-to)	6596-6610
Number of pages	15
Journal	Dalton Transactions
Volume	48
Issue number	19
Early online date	4 Apr 2019
DOIs	https://doi.org/10.1039/c9dt00876d
Publication status	Published - 21 May 2019

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title = "A [C1 + C2] route to propargylidyne complexes",

abstract = "The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with a range of terminal alkynes (RCCH), mediated by [Pd(PPh3)4] and CuI, afford new proparylidynes [W(C-CCR)(CO)2(Tp∗)] [R = tBu, C6H4X (X = H, NH2, NO2), ferrocenyl, APh3 (A = C, Si, Ge), B(O2CCH2)2NMe]. Similar treatment of [W(CBr)(CO)2(Tp∗)] with Ph2Si(CCH)2 affords the ditungstaoctatetrayne [W2(μ-C6)(CO)4(Tp∗)2] while the bimetallic complex [W2\{μ-(CCC)2SiPh2\}(CO)4(Tp∗)2], which is obtained from [W(CBr)(CO)2(Tp∗)] and Ph2Si(CCSnPh3)2, reacts with [AuCl(THT)] (THT = tetrahydrothiophene) to provide the tetrametallic complex [W2Au2\{μ-(CCC)2SiPh2\}Cl2(CO)4(Tp∗)2].",

keywords = "Polynuclear metal-complexes, Transition-metal, Bridging carbene, Carbyne ligands, Bis(tricarbido) complex, Alkylidyne complexes, Tricarbido complexes, Tungsten complexes, Chemistry, Molybdenum",

author = "Hill, \{Anthony F.\} and Manzano, \{Richard A.\}",

note = "{\textcopyright} 2019 The Author(s).",

year = "2019",

month = may,

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doi = "10.1039/c9dt00876d",

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volume = "48",

pages = "6596--6610",

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TY - JOUR

T1 - A [C1 + C2] route to propargylidyne complexes

AU - Hill, Anthony F.

AU - Manzano, Richard A.

PY - 2019/5/21

Y1 - 2019/5/21

N2 - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with a range of terminal alkynes (RCCH), mediated by [Pd(PPh3)4] and CuI, afford new proparylidynes [W(C-CCR)(CO)2(Tp∗)] [R = tBu, C6H4X (X = H, NH2, NO2), ferrocenyl, APh3 (A = C, Si, Ge), B(O2CCH2)2NMe]. Similar treatment of [W(CBr)(CO)2(Tp∗)] with Ph2Si(CCH)2 affords the ditungstaoctatetrayne [W2(μ-C6)(CO)4(Tp∗)2] while the bimetallic complex [W2{μ-(CCC)2SiPh2}(CO)4(Tp∗)2], which is obtained from [W(CBr)(CO)2(Tp∗)] and Ph2Si(CCSnPh3)2, reacts with [AuCl(THT)] (THT = tetrahydrothiophene) to provide the tetrametallic complex [W2Au2{μ-(CCC)2SiPh2}Cl2(CO)4(Tp∗)2].

AB - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with a range of terminal alkynes (RCCH), mediated by [Pd(PPh3)4] and CuI, afford new proparylidynes [W(C-CCR)(CO)2(Tp∗)] [R = tBu, C6H4X (X = H, NH2, NO2), ferrocenyl, APh3 (A = C, Si, Ge), B(O2CCH2)2NMe]. Similar treatment of [W(CBr)(CO)2(Tp∗)] with Ph2Si(CCH)2 affords the ditungstaoctatetrayne [W2(μ-C6)(CO)4(Tp∗)2] while the bimetallic complex [W2{μ-(CCC)2SiPh2}(CO)4(Tp∗)2], which is obtained from [W(CBr)(CO)2(Tp∗)] and Ph2Si(CCSnPh3)2, reacts with [AuCl(THT)] (THT = tetrahydrothiophene) to provide the tetrametallic complex [W2Au2{μ-(CCC)2SiPh2}Cl2(CO)4(Tp∗)2].

KW - Polynuclear metal-complexes

KW - Transition-metal

KW - Bridging carbene

KW - Carbyne ligands

KW - Bis(tricarbido) complex

KW - Alkylidyne complexes

KW - Tricarbido complexes

KW - Tungsten complexes

KW - Chemistry

KW - Molybdenum

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U2 - 10.1039/c9dt00876d

DO - 10.1039/c9dt00876d

M3 - Article

C2 - 31017161

SN - 1477-9226

VL - 48

SP - 6596

EP - 6610

JO - Dalton Transactions

JF - Dalton Transactions

IS - 19

ER -

A [C₁ + C₂] route to propargylidyne complexes

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