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

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