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.
Diazoalkane complexes [Ru(η 5 -C 5 H 5 )-(N 2 CAr1Ar2)(PPh 3 )L]BPh 4 (1, 2; Ar1 = Ph, Ar2 = p-tolyl; Ar1Ar2 = C 12 H 8 ; L = P(OMe) 3 , P(OEt) 3 ) were prepared by allowing compounds RuCl(η 5 -C 5 H 5 )(PPh 3 )L to react with diazoalkane in ethanol. Treatment of complexes 1 and 2 with ethylene under mild conditions (1 atm, room temperature) led not only to the ethylene complexes [Ru(η 5 -C 5 H 5 )(η 2 -CH 2 CH 2 )(PPh 3 )L]BPh 4 (5, 6) but also to dipolar (3 + 2) cycloaddition, affording the 3H-pyrazole derivatives [Ru(η 5 -C 5 H 5 ){η 1 -NNC(Ar1Ar2)CH 2 CH 2 }(PPh 3 )L]BPh 4 (3, 4).The propylene complexes [Ru(η 5 -C 5 H 5 )(η 2 -CH 3 CHCH 2 )(PPh 3 )L]BPh 4 (7, 8) were also prepared. The compounds were characterized by spectroscopy and by X-ray crystal structure determinations of 2a, 3b, and 7.
Mono‐ 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).
CO reacts with FeClz or FeBr2 solutions containing an excess of P(OR)3 (R: Me, Et) to give a mixture of cis and trans derivatives (I) and (II) which can be separated by fractional crystallization.
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