论文信息 - Novel behaviour of dialkylamino-substituted propargylic alcohols in reactions with arene ruthenium(II) complexes

Novel behaviour of dialkylamino-substituted propargylic alcohols in reactions with arene ruthenium(II) complexes

Reaction of arene ruthenium(II) derivatives (C6Me4R2)RuCl2(L)(R = H, Me; L = PMe3, PPh3) with the prop-2-ynylic alcohol derivative HCC–C(H)(OH)(C6H4-p-NMe2) in dichloromethane results in the formation of new oxametallacyclic ruthenium(II) complexes {(C6Me4R2)Ru[CHC(C6H4-p-NMe2)CHO](L)} PF6via an unprecedented 1,2-migration of the dimethylaminophenyl substituent; the structure of one compound (R = H; L = PPh3) is determined by an X-ray crystal structure analysis.

[1] C. Rickard,et al. Activation of 2-propyn-1-ol derivatives by (arene)ruthenium(II) complexes: new route to (alkenylcarbene)- and (polyenylcarbene)-metal complexes , 1992 .

[2] A. Vegas,et al. Ruthenium‐containing Cumulenes: Generation of 2,3,4‐Pentatrienylidene‐ and 3‐Oxo‐l,4‐pentadienyl‐Complexes , 1990 .

[3] G. Olah,et al. Stable carbocations. 195. Rearrangement of ethylenebenzenium ions to .alpha.-phenylethyl(styryl) cations. Determination of the relative energies of the .sigma.-bridged ethylenebenzenium ion, the open-chain 2-phenylethyl cation, and the .alpha.-styryl cation , 1976 .

[4] J. Ibers,et al. Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-C1,O)tris(triphenylphosphine)ruthenium(II) , 1976 .

[5] G. Olah,et al. Stable carbocations. CXXV. Proton and carbon-13 magnetic resonance studies of phenylcarbenium ion (benzyl cations). Effect of substituents of the stability of carbocations , 1972 .

[6] G. Olah,et al. Stable carbonium ions. XXXI. p-Anisonium and methylphenonium ion-formation via aryl participation in strong acid solution , 1967 .

[7] D. Cram. Studies in Stereochemistry. V. Phenonium Sulfonate Ion-pairs as Intermediates in the Intramolecular Rearrangements and Solvolysis Reactions that Occur in the 3-Phenyl-2-butanol System , 1952 .