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

Trichlorostannyl complexes M(SnCl 3 )(Tp)L(PPh 3 ) (1, 2) and M(SnCl 3 )(Cp)L(PPh 3 ) (5, 6) [M ) Ru, Os; L ) P(OMe) 3 (a), P(OEt) 3 (b), PPh(OEt) 2 (c), PPh 3 (d)] were prepared by allowing chloro complexes MCl(Tp)L(PPh 3 ) and MCl(Cp)L(PPh 3 ) to react with an excess of SnCl 2 • 2H 2 O in ethanol. Treatment of trichlorostannyl complexes 1, 2, 5, and 6 with NaBH 4 in ethanol yielded tin trihydride derivatives M(SnH 3 )(Tp)L(PPh 3 ) (3, 4) and M(SnH 3 )(Cp)L(PPh 3 ) (7, 8). Reaction of these complexes with CCl 4 gave the trichlorostannyl precursors 1, 2, 5, and 6. Hydridochlorostannyl intermediates Os(SnH 2 Cl)(Tp)[P(OMe) 3 ](PPh 3 ) (9a) and Os(SnHCl 2 )(Tp)[P(OMe) 3 ](PPh 3 ) (10a) were also obtained. Reaction of trihydridostannyl complexes M(SnH 3 )(Tp)L(PPh 3 ) (3, 4) with CO 2 (1 atm) led to hydridobis(formate) derivatives M[SnH{OC(H)dO} 2 ](Tp)L(PPh 3 ) (11). In contrast, reaction of the related complexes M(SnH 3 )(Cp)L(PPh 3 ) (7, 8) with CO 2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [M[Sn{OC(H)dO} 2 (µ-OH)](Cp)L(PPh 3 )] 2 (12, 13). A reaction path for the formation of 12 and 13, involving the mononuclear tin hydride complex M[SnH{OC(H)dO} 2 ](Cp)L(PPh 3 ), is discussed. The X-ray crystal structure of 12b is reported. Chlorobis(methyl)stannyl Ru(SnClMe 2 )(Cp)[P(OEt) 3 ](PPh 3 ) (15b) and trimethylstannyl complexes M(SnMe 3 )(Tp)[P(OMe) 3 ](PPh 3 ) (14a) and M(SnMe 3 )(Cp)[P(OEt) 3 ](PPh 3 ) (16b, 17b) were prepared by allowing trichlorostannyl compounds 1, 2, 5, and 6 to react with MgBrMe in diethyl ether. Trialkynylstannyl derivatives M[Sn(CtCR) 3 }(Tp)L(PPh 3 ) (18, 19) and Ru[Sn(CtCR) 3 }(Cp)[P(OEt) 3 ](PPh 3 ) (20b) (R ) Ph, p-tolyl) were also prepared from the reaction of trichlorostannyl complexes 1, 2, 5, and 6 with Li + (CtCR)in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determination of Ru(SnClMe 2 )(Cp)[P(OEt) 3 ](PPh 3 ) (15b).

Hydride complexes MnH(CO)3P2 (1), MnH(CO)2P3 (2), and MnH(CO)P4 (3) (P = P(OEt)3 (a), PPh(OEt)2 (b), PPh2OEt (c), PPh(OiPr)2 (d) were prepared by allowing the MnH(CO)5 species to react with an excess of phosphine upon UV irradiation or under reflux conditions. Their formulation and geometry in solution were established by IR and 1H, 13C, and 31P NMR spectroscopy. Protonation reactions with HBF4·Et2O of the monocarbonyls MnH(CO)P4 (3) afford isolable dihydrogen derivatives [Mn(η2-H2)(CO)P4]BPh4 (5), which were characterized by variable-temperature 1H and 31P NMR spectra, T 1 measurements, and J HD values. Thermally unstable (above 0 °C) [Mn(η2-H2)(CO)2P3]+ (4) cations were also prepared by protonation of the dicarbonyl hydrides MnH(CO)2P3 (2) and fully characterized in solution. Evolution of H2 from 4 and 5 results in the formation of the unsaturated complexes [Mn(CO)2P3]BPh4 (6) and [Mn(CO)P4]BPh4 (7), which are probably stabilized by an agostic interaction between the metal center and a C−H proton of the phosphite. Treatment of the unsaturated complexes 6 and 7 and of the triflate compounds [Mn(η1-OSO2CF3)(CO)3P2] (8) with Li+RC⋮C- gave the new acetylide derivatives [Mn(C⋮CR)(CO)P4] (9), [Mn(C⋮CR)(CO)2P3] (10), and [Mn(C⋮CR)(CO)3P2] (11) (R = Ph, p-tolyl). The new series of cationic manganese compounds [Mn(CO)2(p-tolylCN)P3]BPh4 (12), [Mn(CO)(p-tolylCN)P4]BPh4 (13), [Mn(CO)2(p-tolylNC)P3]BPh4 (14), [Mn(CO)(p-tolylNC)P4]BPh4 (15), [Mn(CO)3P3]BPh4 (16), and [Mn(CO)2P4]BPh4 (17) were also obtained by reacting the unsaturated compounds 6 and 7 with the appropriate ligands.

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Bis(alkyny1) complexes Ru(CWR12P4 (1-3) (R = Ph,p-tolyl, tBu; P = P(OMe)3 (11, P(OEt)3 (2), PPh(0Et)z (3)) were prepared by reacting RuCl2P4 with excess Lif RC=C-, and a trans geometry was established both in solids (X-ray) and in solution. The reaction of these alkynyls (1 -3) with electrophilic reagent depends on the nature of the phosphite ligand. Vinylidene-acetylide derivatives [RU(CGCR){=C=C(R~)R}P~I+ (R1 = H (4, 51, CH3 (7, 8), ArN-N (lo), I (12), 2,3-(No~)&&S (14)) were prepared with P(OMe)3 and P(OEt)3 ligand by treatment of 1 and 2 with HBF4, CF3S03Me, ArNz+BF4-, Iz, and ~,~-( N O Z ) Z C~H~S C~, respectively. Instead, only the diazo-and iodovinylidenes [Ru(CsCR){ =C=C(R1)R)P41f (RI = p-tolN-N (ll), I (13)) were obtained with the PPh(0Et)z phosphite ligand. These vinylidene compounds were fully characterized by IR, IH, 31P, and 13C NMR spectra, and a single-crystal X-ray structure determination of complex [Ru(C=CPh){=C=C(Me)Ph}-{P(OEt)3}4]CF3S03 (8a) is reported. The alkynyl-vinylidene [Ru(C=CR){=C=C(H)R}P4]+ cations (4, 5) rearrange in solution to enynyl [Ru(q3-RC3CHR)P41f derivatives, and the reaction is inhibited by the presence of free alkyne. Kinetic data support a mechanism involving a pentacoordinate intermediate formed by loss of the vinylidene ligand. Substitution of the =C=C(H)R ligand by phosphite, isocyanide, and nitrile is easy in 4 and 5 and leads to [Ru(C~CPh){P(OMe~3}P41+ -(17), tolCN)2P4l2+ (19) (P = P(OEt)3), derivatives. ligand in 4 and 5, giving Ru(C=CR)zP4, was Introduction A large number of studies on the chemistry of transi-