Reactions of Imidazolio‐Phosphides with Organotin Chlorides: Surprisingly Diverse

Reactions of primary imidazolio-phosphides (“imidazolylidene-phosphinidenes”) with R2SnCl2 yield as main products spectroscopically detectable Lewis pairs which undergo base-induced dehydrochlorination in the presence excess dichlorostannane to afford zwitterionic chloride adducts distannylated imidazolio-phosphines. In contrast, reactions R3SnCl proceed under dismutation furnish mixtures containing imidazolium salts and stannylated (oligo)phosphines P(SnR3)3 P7(SnR3)3, respectively. DFT studies were used rationalize divergent behavior based on presumption that thermodynamic control observed represent most stable species specific reaction conditions. Computational simulation selected steps provides a model mechanism for Lewis-acid promoted creation PP-bonds, is prerequisite oligophosphine formation. The computational further highlight parallels between Brønsted acids, allow also extrapolate P-nucleophiles towards other electrophiles than organotin chlorides.