Stannyl Complexes of Rhodium and Iridium: Preparation of Mono‐ and Bis(trihydridestannyl) Derivatives

Abstract

AbstractMono‐ and bis(trichlorostannyl) complexes [MCl(SnCl3)(η5‐C5Me5){P(OR)3}] (1, 2) and [M(SnCl3)2(η5‐C5Me5){P(OR)3}] (3, 4) (M = Rh, Ir; R = Me, Et) were prepared by allowing chloro compounds MCl2(η5‐C5Me5)[P(OR)3] to react with anhydrous SnCl2 in refluxing 1,2‐dichloroethane. Treatment of trichlorostannyl complexes of iridium 2 and 4 with NaBH4 in ethanol afforded hydride‐trihydridestannyl derivatives [IrH(SnH3)(η5‐C5Me5){P(OR)3}] (5) and bis(trihydridestannyl) [Ir(SnH3)2(η5‐C5Me5){P(OR)3}] (6), the reaction of which with methylpropiolate HC≡CCOOMe led to trivinylstannyl derivatives [IrH{Sn[C(COOMe)=CH2]3}(η5‐C5Me5){P(OMe)3}] (7 a) and [Ir{Sn[CH=C(H)COOMe]3}2(η5‐C5Me5){P(OMe)3}] (8 a). The complexes were characterised spectroscopically (IR and 1H, 31P, 13C, 119Sn NMR) and by X‐ray crystal structure determination of [Ir(SnCl3)2(η5‐C5Me5){P(OMe)3}] (4 a).