Synthesis and reactivity of an anionic allenylidene complex. Issue 5 (12th January 2018)

• Record Type: Journal Article
• Authors: Hill, Anthony F.; Manzano, Richard A.
• Is Part Of: Dalton transactions. Volume 47:Issue 5(2018)
• Page Start: 1412
• Page End: 1416
• Publication Date: 2018-01-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt04576j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The reaction of [W(CCCSiMe3 )(CO)2 (Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe3 )(CO)2 (Tp*)] which reacts with electrophiles (H +, Me + ) at the β-carbon to afford vinylcarbyne complexes and with bromine via oxidative C–C coupling at the β-carbon. Abstract : The reaction of [W(CCCSiMe3 )(CO)2 (Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with MeLi generates the first example of an anionic allenylidene complex Li[W(CCCMeSiMe3 )(CO)2 (Tp*)] which reacts with electrophiles (H +, Me + ) at the β-carbon to afford vinylcarbyne (allylidyne) complexes [W(CCECMeSiMe3 )(CO)2 (Tp*)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(CMeSiMe3 )CW(CO)2 (Tp*)}2 via oxidative C–C coupling at the β-carbon.