| The [(η6-arene)RuCl2]2 [arene = 1,3,5-Me3C6H3 (1), p-MeC6H4CHMe2 (2), 1,2,4,5-C6Me4 (3), C6Me 6 (4), p-MeC6H4Me (5) and MeC6H5 (6)] dimers undergo base-promoted hydroalkylation reactions with KOtBu and diphenylvinylphosphine in refluxing acetonitrile to produce tethered complexes of the type [{lcub}η6-2,4,5-Me3H2C 6-1-CH2CH2CH2P(C6H 5)2{rcub}RuCl2] (3b).; The complexes [(η6-arene)Ru(Ph2PCH=CH 2)Cl2] [arene = 1,2,4,5-Me4H2C 6, Me6C6] and [(η6-1,2,4-Me 3H2C6-5-CH2CH2CH2P(C 6H5)2)RuCl2] react with terminal alkynes and propargyl alcohols in the presence of NaPF6 in methanol yielding alkoxy carbenes of the type [(η6-arene)Ru{lcub}=C(OMe)(R){rcub}(Ph 2PCH=CH2)(Cl)]PF6 (R = CH3, ( 1a); CH2Ph, (2a); CH2(cyclo -C6H9) (4b); CH(cyclo -C5H8) (5b)), and [(η 6-1,2,4,5-Me4H2C6CH2CH 2-CH2P(C6H5)2)Ru{lcub}=C(OMe)(R){rcub}(Cl)]PF 6 (R = CH3 (1b), CH2Ph (2b ); CH=Ph2 (3b)). Isocyanide complexes of the type [(η6-arene)Ru(DPVP)(CNPh)(Cl)]PF6 have also been synthesized.; The complexes [(η6-arene)RuCl2(R2 AsCH=CH2)], [arene = MeC6H5, R = Ph (1a), R = Cy (1b); p-MeC6 H4Me, R = Ph (2a), R = Cy (2b); o-MeC6H4Me, R = Ph (3a), R = Cy (3b); 1,3,5-Me3C6H3, R = Ph (4a); p-MeC6H4CHMe 2, R = Ph (5a), R = Cy (5b); 1,2,4,5-Me 4C6H2, R = Ph (6a), R = Cy ( 6b); C6Me6, R = Ph (7a)] have been synthesized by reacting [(η6-arene)RuCl2] 2 dimers with the respective vinylarsine.; In the presence of AgPF6, in a 1:1 dichloromethane/acetone solvent mixture the compound [(η6-C6Me 6)RuCl2(Cy2PCH=CH2)] afforded [(η 6-C6Me6)RuCl(η3-DCVP)]PF 6 (1b). Reaction of [(η6-C6Me 6)RuCl2(Ph2PCH=CH2)] yielded the unexpected trinuclear hetero-bimetallic complex [{lcub}(η6-C6Me 6)Ru(μ-Cl)2(Ph2PCH=CH2){rcub}2Ag](PF 6) (3b) the structure of which was determined by X-ray crystallography. (1b) reacts with phenylisocyanide and 1,1-diphenylpropargyl-1-ol to form [(η6-C6Me6)RuCl(η 1-DCVP) (CNPh)]PF6 and the unstable [(η6-C 6 |
