Inorganic Chemistry, Vol.42, No.23, 7644-7651, 2003
Synthesis 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) (1:11). The crystal structures of 5 and [Ag{H2NC(Me)(2)CH2C(O)Me}(PTo(3))]ClO4 (A), a product obtained in a reaction between NH3, AgClO4, and PTo(3), have been determined.