Synthesis and reactivity of an anionic allenylidene complex

Abstract

The reaction of [W(equivalent to CC equivalent to 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 beta-carbon to afford vinylcarbyne (allylidyne) complexes [W(equivalent to CCE=CMeSiMe3)(CO)(2)(Tp*)] (E = H, Me), and with bromine provides the unprecedented binuclear bis(carbyne) complex {C(=CMeSiMe3)C equivalent to W(CO)(2)(Tp*)}(2) via oxidative C-C coupling at the beta-carbon. Show more