THE SYNTHESIS AND CHARACTERIZATION OF AN ORTHO-METALATED CARBENERUTHENIUM(II) COMPLEX, CONTAINING A METALATED NORMAL-BENZYL SUBSTITUENT WITH A 6-MEMBERED METALATE NUCLEUS, CRYSTAL-STRUCTURE OF [RUCL(CN(CH2C6H5)CH2CH2NCH2C6H4)(PPH3)2]

The complex [RuCl(H)(PPh3)3] reacts with the tetra-benzyl substituted electron-rich alkene [ = CN(CH2Ph)CH2CH2NCH2Ph]2 with elimination of H-2 and PPh3 to form the five Coordinate carbeneruthenium(II) complex, abbreviated as [RuCl(LBx)(PPh3)2] (1), containing a 6 membered metallate nucleus, via ortho-metallation of one of the N-benzyl substituents. Reaction with PEt3 gives the unusual bisphosphine complex [RuCl(LBz)(PEt3)(PPh3)] which contains a chiral metal atom. Small pi-acceptor ligands (e.g. CO, P(OMe)3) add to form stable 6-coordinate complexes. C-13 NMR spectroscopic data provides information on the stereochemistry of the molecules as 2J(C-13-P-31)trans much greater than 2J(C-13-P-31)cis. The complexes appear stereochemically rigid in solution at 25-degrees. The crystal structure of the title compound has been determined. The two Ru-C(sp2) distances are 1.968 (6) angstrom [Ru-C(carb)] and 2.014 (7) angstrom [Ru-C(aryl)2].