SYNTHESIS, CHARACTERIZATION, REACTIVITY AND STRUCTURE OF SOME MONO AND BINUCLEAR (ETA(6)-P-CYMENE)RUTHENIUM(II) COMPLEXES

Reactions of [{Ru(eta(6)-C10H14)Cl-2}(2)] (eta(6)-C10H14 = p-cymene H3 C-C6H4-CH(CH3)(2)) with 4-cyanopyridine (referred hereafter as CNPy) i n 1:1 and 1:2 molar ratios in dichloromethane yields the binuclear com plex [{Ru(eta(6)-C10H14)Cl-2}(2)(mu-CNPy)] and the mononuclear complex [Ru(eta(6)-C10H14)Cl-2(CNPy)]. The latter complex further reacts with [{Ru(eta(6)-C6Me6)Cl-2}(2)] and [Ru(eta(5)-C5H5)(PPh3)(2)Cl] to give 4-cyanopyridine bridged complexes Cl-2(eta(6)-C10H14)Ru(mu-CNPy)Ru(mu( 6)-C6Me6)Cl-2] and [Cl-2(eta(6)- C10H14)Ru(mu-CNPy)Ru(eta(5)-C5H5)(PPh 3)(2)](+). The complex [Ru(eta(6)-C10H14)Cl-2(CNPy)] also undergoes me tathetical reactions with EPh3 (E = P, As or Sb) to give complexes wit h the general formulations [Ru(eta(6)-C10H14)Cl-2(EPh3)], however its reaction with diphenylphosphinomethane (dppm) in a 1:1 ratio gives the mononuclear complex [Ru(eta(6)-C10H14)Cl-2(dppm)] in which the dppm l igand is present in uncommon coordination mode (eta(1)-dppm). The reac tion products have been characterized by microanalyses and spectroscop ic studies (IR, H-1- C-13-, P-31-NMR). The structure of [Ru(eta(6)-C10 H14)Cl-2(CNPy)] [a = 10.984(1), b = 14.052(1), c = 12.189(1) Angstrom; beta = 114.810(1)degrees; V = 1707.8(4) Angstrom(3); D-calc = 1.596 g cm(-3); monoclinic P2(1)/c; Z = 4] and confirmation of uncommon coord ination mode of dppm, in [Ru(eta(6)-C10H14)Cl-2(dppm)] [a = 11.504(3), b = 19.532(3), c = 15.942(3) Angstrom; beta = 96.08(2)degrees; V = 35 62(2) Angstrom(3); D-calc = 1.446 g cm(-3); monoclinic P2(1)/n; Z = 4] has been determined by X-ray crystallography. (C) 1998 Elsevier Scien ce S.A, All rights reserved.