Carbodiphosphoranes (CDPs) are divalent carbon[0] compounds with unusual electronic properties that make them highly reactive and unstable. CDPs have historically been used as strong sigma donors in organometallic complexes. Recent experimental work, however, have shown for the first time the use of CDPs as effective catalysts in the hydroboration of ketones and imines, rivaling other common Lewis base catalysts. Mechanistic details into the activation modes and consequent catalytic reduction afforded by CDPs are unknown. In this work, we use density functional theory methods to investigate several plausible mechanisms stemming from the CDP-substrate adducts formed in the reaction and reveal which catalytic pathway is energetically likely. Detailed analyses of developing charges and frontier molecular orbitals reveal why carbodiphosphoranes are effective Lewis-base catalysts, even when challenging substrates are employed.

Mechanistic insights into the use of carbodiphosphoranes as Lewis-base catalysts

ACS Spring 2022

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