Synthesis and reactivity of an anionic allenylidene complex

Anthony F. Hill; Richard A. Manzano

doi:10.1039/c7dt04576j

Synthesis and reactivity of an anionic allenylidene complex

Anthony F. Hill^*, Richard A. Manzano

^*Corresponding author for this work

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

9 Citations (Scopus)

Abstract

The reaction of [W(CCCSiMe₃)(CO)₂(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe₃)(CO)₂(Tp∗)] which reacts with electrophiles (H⁺, Me⁺) at the β-carbon to afford vinylcarbyne (allylidyne) complexes [W(CCECMeSiMe₃)(CO)₂(Tp∗)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(CMeSiMe₃)CW(CO)₂(Tp∗)}₂via oxidative C-C coupling at the β-carbon.

Original language	English
Pages (from-to)	1412-1416
Number of pages	5
Journal	Dalton Transactions
Volume	47
Issue number	5
DOIs	https://doi.org/10.1039/c7dt04576j
Publication status	Published - 2018

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abstract = "The reaction of [W(CCCSiMe3)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe3)(CO)2(Tp∗)] which reacts with electrophiles (H+, Me+) at the β-carbon to afford vinylcarbyne (allylidyne) complexes [W(CCECMeSiMe3)(CO)2(Tp∗)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(CMeSiMe3)CW(CO)2(Tp∗)}2via oxidative C-C coupling at the β-carbon.",

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AU - Manzano, Richard A.

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N2 - The reaction of [W(CCCSiMe3)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe3)(CO)2(Tp∗)] which reacts with electrophiles (H+, Me+) at the β-carbon to afford vinylcarbyne (allylidyne) complexes [W(CCECMeSiMe3)(CO)2(Tp∗)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(CMeSiMe3)CW(CO)2(Tp∗)}2via oxidative C-C coupling at the β-carbon.

AB - The reaction of [W(CCCSiMe3)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe3)(CO)2(Tp∗)] which reacts with electrophiles (H+, Me+) at the β-carbon to afford vinylcarbyne (allylidyne) complexes [W(CCECMeSiMe3)(CO)2(Tp∗)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(CMeSiMe3)CW(CO)2(Tp∗)}2via oxidative C-C coupling at the β-carbon.

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DO - 10.1039/c7dt04576j

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VL - 47

SP - 1412

EP - 1416

JO - Dalton Transactions

JF - Dalton Transactions

IS - 5

ER -

Synthesis and reactivity of an anionic allenylidene complex

Abstract

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