The complexes (η 6 -C 6 Me 6 )Cl 2 Ru(PR 3 ) ( 1; PR 3 = DPVP (diphenylvinylphosphine) ( a ), PMe 3 ( b ), PPh 3 ( c )) react with NaPF 6 in acetonitrile solutions to give the cationic complexes [(η 6 -C 6 Me 6 )ClRu(PR 3 )(NCCH 3 )]PF 6 ( 2a − c ) by loss of NaCl. Complexes 1a and 2a react with HC⋮CSiMe 3 and HC⋮CPh (and NaPF 6 for 1a ) in MeOH to give the carbene complexes [(η 6 -C 6 Me 6 )Cl(DPVP)Ru C(OCH 3 )CH 3 ]PF 6 ( 3a ) and [(η 6 -C 6 Me 6 )Cl(DPVP)Ru C(OCH 3 )CH 2 Ph]PF 6 ( 4a ), respectively. The known analogues 3b, c and 4b and the new complex 4c have been synthesized from 2b, c and HC⋮CR. The solid-state structures of these complexes show a wide variation in the orientation of the carbene plane with respect to the plane of the η 6 -arene ring (dihedral angles of 37.9−59.6°). The solution dynamic behavior of 3a − c and 4a − c is discussed. Complex 2a also reacts with HC⋮CCH 2 CH 2 OH in MeOH to give the oxacyclic carbene complex ( 5 ). 1a (and NaPF 6 ) and 2a react with HC⋮CC(OH)Ph 2 in MeOH to give the novel phosphorus ylide complex ( 6 ) and with dimethylpropargylamine in CH 2 Cl 2 or dichloroethane to give the amino cyclic carbene complex ( 7 ) and the metallacyclic complex ( 8 ). In the absence of MeOH, reaction of 2a with HC⋮CC(OH)Ph 2 gives the dimeric complex [(η 6 -C 6 Me 6 )Ru(μ-Cl) 3 Ru(η 6 -C 6 Me 6 )]PF 6 . Complex 2a plus HC⋮CPh in the absence of MeOH gives the carbonyl complex [(η 6 -C 6 Me 6 )Cl(DPVP)Ru(CO)]PF 6 ( 9 ). Reaction of 2c with HC⋮CPh in MeOH for extended time periods (>1 day) gives an analogous carbonyl complex of PPh 3, [(η 6 -C 6 Me 6 )Cl(PPh 3 )Ru(CO)]PF 6 . All complexes have been characterized by 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR and IR spectroscopies and electrochemistry and in most cases by X-ray crystallography. Complex 1a is an efficient catalyst for the regioselective addition of H 2 O to HC⋮CPh, producing exclusively acetophenone in 70% isolated yield.
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Hansen et al. (2000) studied this question.