ynthesis of [Ag(NH=CMe2)2]ClO4 and Its Use as a Source of Acetimine. 1. Synthesis of the First Acetimine Rhodium Complexes and the First Crystal Structure of a Diacetonamine Complex

The reaction of AgClO4 and NH3 in acetone gave [Ag(NH=CMe2)2]ClO4 (1). The reactions of 1 with [RhCl(diolefin)]2 or [RhCl(CO)2]2 (2:1) gave the bis(acetimine) complexes [Rh(diolefin)(NH=CMe2)2]ClO4 [diolefin = 1,5 cyclooctadiene = cod (2), norbornadiene = nbd (3)] or [Rh(CO)2(NH=CMe2)2]ClO4 (4), respectively. Mono(acetimine) complexes [Rh(diolefin)(NH=CMe2)(PPh3)]ClO4 [diolefin = cod (5), nbd (6)] or [RhCl(diolefin)(NH=CMe2)] [diolefin = cod (7), nbd (8)] were obtained by reacting 2 or 3 with PPh3 (1:1) or with Me4NCl (1:1.1), respectively. The reaction of 4 with PR3 (R = Ph, To, molar ratio 1:2) led to [Rh(CO)(NH=CMe2)(PR3)2]ClO4 [R = Ph (9), C6H4Me-4 = To (10)] while cis-[Rh(CO)(NH=CMe2)2(PPh3)]ClO4 (11) was isolated from the reaction of 1 with [RhCl(CO)(PPh3)]2 (1:1). The crystal structures of 5 and [Ag{H2NC(Me)2CH2C(O)Me}(PTo3)]ClO4 (A), a product obtained in a reaction between NH3, AgClO4, and PTo3, have been determined.