Hydride complexes IrHCl(2)(PiPr(3))P(2) (1) and IrHCl(2)P(3) (2) [P = P(OEt)(3) and PPh(OEt)(2)] were prepared by allowing IrHCl(2)(PiPr(3))(2) to react with phosphite in refluxing benzene or toluene. Treatment of IrHCl(2)P(3), first with HBF(4).Et(2)O and then with an excess of ArCH(2)N(3), afforded benzyl azide complexes [IrCl(2)(eta(1)-N(3)CH(2)Ar)P(3)]BPh(4) (3, 4) [Ar = C(6)H(5), 4-CH(3)C(6)H(4); P = P(OEt)(3), PPh(OEt)(2)]. Azide complexes reacted in CH(2)Cl(2) solution, leading to the imine derivative [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}P(3)]BPh(4) (5). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [IrCl(2)(eta(1)-N(3)CH(2)C(6)H(5)){P(OEt)(3)}(3)]BPh(4) (3a) and [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}{P(OEt)(3)}(3)]BPh(4) (5a). Both solid-state structure and (15)N NMR data indicate that the azide is coordinated through the substituted Ngamma [Ir]-Ngamma(CH(2)Ar)NNalpha nitrogen atom.

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Tin trihydride Os(SnH3)(Tp)L(PPh3) [L = P(OMe)3, P(OEt)3] complexes were prepared by allowing chloro OsCl(Tp)L(PPh3) complexes to react first with SnCl2 and then with NaBH4 in ethanol. The complexes were characterized spectroscopically and by the X-ray crystal structure determination of the Os(SnH3)(Tp){P(OMe)3}(PPh3) derivative. Reaction of tin trihydride complexes with CO2 led to formate Os[SnH{OC(H)=O}2](Tp)L(PPh3) derivatives

The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C≡CH) yielded the trialkynylstannyl derivatives M[Sn(C≡CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C≡CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C≡CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)=O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate Re[SnH{OC(H)=O}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported