Cleavage of the Au−P Bond in Au‐Substituted Phosphines

Abstract Three protocols that involve the cleavage of the Au−P bond in Au‐substituted phosphines (AuPhos) have been demonstrated, namely i) direct demetallation with a strong anionic base; ii) protonation followed by demetallation with a neutral base; iii) oxidation‐triggered metal migration. Specifically, direct demetallation of (CAAC)AuPPh 2 ( 1 a ) (CAAC=cyclic (alkyl)(amino)carbene) with KP(TMS) 2 or LiC(N 2 )TMS yields (CAAC)AuPTMS 2 ( 2 ) or (CAAC)AuC(N 2 )TMS ( 3 ), respectively. Treatment of (NHC)AuPPh 2 ( 1 b ) (NHC=N‐heterocyclic carbene) with HOTf followed by the corresponding neutral phosphine gives scarce examples of aurophosphonium salts [(NHC)AuPHAd 2 ][OTf] ( 5 ) and [((NHC)Au) 2 PPh 2 ][OTf] ( 6 ). Oxidation of 1 a or 1 b with Se affords LAuSeP(Se)Ph 2 (L=CAAC, 7 a ; NHC, 7 b ).