Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P2N-Ring Ligand

Synthesis of 1,1′‐bifunctional aminophosphane complexes 3 a–e was achieved by the reaction of Li/Cl phosphinidenoid complex 2 with various primary amines (R=Me, iPr, tBu, Cy, Ph). Deprotonation of complex 3 a (R=Me) with potassium hexamethyldisilazide yielded a mixture of K/NHMe phosphinidenoid complex 4 a and potassium phosphanylamido complex 4 a′. Treatment of complex 3 c (R=tBu) and e (R=Ph) with KHMDS afforded the first examples of K/NHR phosphinidenoid complexes 4 c and e. The reaction of complex 3 c with 2 molar equivalents of KHMDS followed by PhPCl2 afforded complexes 5 c,c′, which possess a P2N‐ring ligand. All complexes were characterized by NMR, IR, MS, and microanalysis, and additionally, complexes 3 b–e and 5 c′ were scrutinized by single‐crystal X‐ray crystallography. Aminophosphane–transition‐metal complexes: Normal N−H bond insertion reactions of a P1 building block with a Li/Cl phosphinidenoid complex I enables the facile access to a series of aminophosphane complexes, which are deprotonated to enable access to the first stable K/NHR phosphinidenoid complexes II. The double deprotonation protocol of an aminophosphane complex in the presence of PhPCl2 offers a new synthetic route to a three‐membered P‐ring ligand system (III; see scheme).