PREPARATION AND REACTIVITY OF DINUCLEAR RUII COMPLEXES WITH BRIDGING THIOLATE LIGANDS [CP-ASTERISK-RU(MU-SR)2RUCP-ASTERISK] (CP-ASTERISK = ETA-5-C5ME5 - R=(I)PR, (T)BU, 2,6-ME2C6H3) - OXIDATIVE ADDITION OF ALKYL-HALIDES AT THE DIRUTHENIUM CENTER

Reactions of [Cp*RuCl]4 (Cp* = eta5-C5Me5) with NaSR (R =(i)Pr, (t)Bu, 2,6-Me2C6H3) in THF afforded dinuclear Ru(II) complexes with two bridging thiolate ligands [Cp*Ru(mu-SR)2RuCp*] (3). An X-ray analysis of 3c (R = 2,6-Me2C6H3) has disclosed the folded Ru2S2 core structure with two equatorial C6H3Me2-2,6 groups in a solid state, while the results of variable-temperature H-1 NMR study are diagnostic of the fluxional nature of complexes 3 in solution resulting from the RU2S2 ring inversion. Complex 3a (R -(i)Pr) underwent oxidative addition of RX (R = PhCH2CH2 or PhCH2, X = Br; R = Me or Et, X = 1) and H-2 across the Ru2 center to give [Cp*RuR(mu-S(i)Pr)2RuCp*X] (7) and [Cp*RuH(mu-S(i)Pr)2RuCp*H], respectively. The structure of 7a (R = PhCH2CH2, X = Br) has been determined by X-ray crystallography. Crystal data for 3c: space group P4(2)/mnm, g = 15.307(4) angstrom, c - 16.070(4) angstrom, V = 3765(2) angstrom3, Z = 4; 7a: space group P2(1)/c, a = 10.348(2) angstrom, b = 15.113(2) angstrom, c = 22.340(5) angstrom, beta = 93.10(2)-degrees, V = 3488(1) angstrom3, Z = 4.