Facile activation of alkynes with a boraguanidinato-stabilized germylene: a combined experimental and theoretical study

Abstract

A boraguanidinato-stabilized germylene, [(i-Pr)₂NB(N-2,6-Me₂C₆H₃)₂]Ge, reacts with alkynes RCCR selectively in a 2 : 1 molar ratio to afford 3,4-R,R′-1,2-digermacyclobut-3-enes 1a–e as the products of formal [2 + 2 + 2] cyclization [R/R′ = Me/Me (1a), Ph/Ph (1b), Ph/H (1c), t-Bu/H (1d) and Cy/H (1e)]. Ferrocenyl-substituted alkynes react similarly, yielding the corresponding ferrocenylated 3,4-R,R′-1,2-digermacyclobut-3-enes 2a–d [where R/R′ = Fc/H (2a), Fc/Me (2b), Fc/Ph (2c), and Fc/Fc (2d); Fc = ferrocenyl]. By contrast, only one of the triple bonds available in conjugated diynes RCCCCR is activated with the germylene, while the second one remains intact even in the presence of an excess of the germylene. The exclusive formation of 3,4-R,(CCR)-1,2-digermacyclobut-3-enes 3a–c [R = Ph (3a), t-Bu(3b), and Fc (3c)] was ascribed to a steric repulsion around the second triple bond. On the other hand, the reaction of the germylene with more flexible dialkyne fc(CCPh)₂ (fc = ferrocene-1,1′-diyl) proceeded in the expected manner, producing compound 4, where both triple bonds are transformed into 1,2-digermacyclobut-3-ene rings by reaction with four equivalents of the germylene. All compounds were characterized by multinuclear NMR spectroscopy, Raman and IR spectroscopy, and in the case of 1a–c, 2a, 2c, 3a, 3b and 4, also by single-crystal X-ray diffraction analysis. The ferrocenyl substituted compounds were studied by cyclic voltammetry (CV). Finally, the plausible reaction pathway was studied for a model reaction of [(i-Pr)₂NB(N-2,6-Me₂C₆H₃)₂]Ge with MeCCMe using DFT computations.