Ph (3b), H (3c), Me (3d)). The formation of complexes 3a-d and 4a-c proceeds through an intramolecular cycloaddition of the CdC allyl and C R dC β bonds in the intermediate allenylidene complexesThe allenylidene complex [Ru(η 5 -C 9 H 7 )(dCdCdCPh 2 ){κ 1 (P)-Ph 2 PCH 2 CHdCH 2 }(PPh 3 )][PF 6 ] (5) has been isolated from the reaction of 2a with 1,1diphenyl-2-propyn-1-ol in CH 2 Cl 2 . The deprotonation of complexes 3a-d and 4a with potassium tert-butoxide gives rise to the neutral complexes [Ru(η 5 -C n H m ){κ 2 (P,C)-{CdC-

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[L = CO, X = SbF 6 , R = CH 2 CH=CH 2 (3a), CH 2 CH 2 CH=CH 2 (3b); L = PPh 3 , X = PF 6 , R = CH 2 CH 2 CH=CH 2 (4b)] have been prepared by treatment of the complexes 1a,b and 2b with a halide abstractor such as AgSbF 6 or NaPF 6 , respectively. Deprotonation reactions of

Conditions for a first oxidative conversion of alkenes into 2-amino ketones are described, which yield racemic products within a direct oxidation pathway and 2-amino ketones with up to 99% enantiomeric excess from the corresponding enantiopure amino alcohols.

The cyclopentadienyl-containing complex [Ru(η5-C5H5)(MeCN){κ3(P,C,C)-Ph2PCH2CHCH2}][PF6] (1) reacts with allenes, giving regioselectively the η2-allene complexes [Ru(η5-C5H5)(MeCN){κ(P)-Ph2PCH2CHCH2}(η2-CH2CCR1R2)][PF6] [R1 = R2 = Me (3); R1 = H, R2 = Ph (4); R1R2 = −(CH2)5– (5)]. On the other hand, the reaction of the pentamethylcyclopentadienyl-containing complex [Ru(η5-C5Me5)(MeCN){κ3(P,C,C)-Ph2PCH2CHCH2}][OTf] (2) with allenes yields regio- and stereoselectively the complexes [Ru(η5-C5Me5){κ(P),η4-Ph2PCH2CHCHC(R1R2)CHCH2}][OTf] [R1 = R2 = Me (6); R1 = H, R2 = Ph (7); R1R2 = −(CH2)5– (8)] via the intermolecular coupling of allene and allyldiphenylphosphine ligands. The intermediate complex [Ru(η5-C5Me5)(MeCN){κ(P)-Ph2PCH2CHCH2}{η2-CH2CCMe2}][OTf] (9) has been spectroscopically characterized. The structure of complex [Ru(η5-C5Me5){κ(P),η4-Ph2PCH2CHCHC(Me)2CHCH2}][{3,5-(CF3)2C6H3}4B] (6a) has been resolved by X-ray diffraction analysis.