The first acetimine gold(I) and gold(III) complexes and the first acetonine complexes

Ketimino(phosphino)gold(I) complexes of the type AuNR=C(Me)R']L]X (X = ClO4, R = H, L = PPh3, R'=Me (la), Et (2a); L=PAr3 (Ar=C6H4OMe-4), R'=Me (1b), Et (2b); L=PPh3, R=R'=Me (3); X= CF3SO3 (OTf), L=PPh3, R=R'=Me (3'); R=Ar, R'=Me (4)) have been prepared from Au(acac)L] (acac = acetyl acetonate) and ammonium salts RNH3]X dissolved in the appropriate ketone MeC(O)R'. Complexes Au(NH=CMe2)2]X (X = C1O4 (6), OTf (6')) were obtained from solutions of Au(NH3)2]X in acetone. The reaction of 6 with PPNAuCl2] or with PhICl2 gave AuCl(NH=CMe2)] (7) or AuCI2(NH=CMe2)2]ClO4 (8), respectively. Complex 7 was oxidized with PhICl2 to give AuCl3(NH=CMe2)] (9). The reaction of AuCl(tht)] (tht = tetrahydrothiophene), NaClO4, and ammonia in acetone gave Au(acetonine)2]ClO4 (10) (acetonine = 2,2,4,4,6-pentamethyl-2,3,4,5-tetrahydropyrimidine) which reacted with PPh3 or with PPNAuCl2] to give Au(PPh3)(acetonine)]ClO4 (11) or AuCl(acetonine)] (12), respectively. Complex 11 reacts with Au(PPh3)(Me2CO)]ClO4 to give (AuPPh3)2(mu-acetonine)](ClO4)2 (13). The reaction of AgClO4 with acetonine gave Ag(acetonine)(OClO3)] (14). The crystal structures of Au(NH2Ar)(PPh3)]OTf (5), 6' and 10 have been determined.