Abstract
Reactions of [Cp★RuCl] 4 (Cp★ η 5-C 5Me 5) with NaSR (R iPr, tBu, 2,6-Me 2C 6H 3) in THF afforded dinuclear Ru II complexes with two bridging thiolate ligands [Cp★Ru(μ-SR) 2RuCp★] ( 3). An X-ray analysis of 3c (R = 2,6-Me 2C 6H 3) has disclosed the folded Ru 2S 2 core structure with two equatorial C 6H 3Me 2-2,6 groups in a solid state, while the results of variable-temperature 1H NMR study are diagnostic of the fluxional nature of complexes 3 in solution resulting from the Ru 2S 2 ring inversion. Complex 3a (R iPr) underwent oxidative addition of RX (R PhCH 2CH 2 or PhCH 2, X Br; R Me or Et, X I) and H 2 across the Ru 2 center to give [Cp★RuR(μ-S iPr) 2RuCp★X] ( 7) and [Cp★RuH(μ-S iPr) 2RuCp★H], respectively. The structure of 7a (R PhCH 2CH 2, X Br) has been determined by X-ray crystallography. Crystal data for 3c: space group P4 2/ mnm, a = 15.307(4) Å, c = 16.070(4) Å, V = 3765(2) Å 3, Z = 4; 7a: space group P2 1/ c, a = 10.348(2) Å, b = 15.113(2) Å, c = 22.340(5) Å, β = 93.10(2)°, V = 3488(1) Å 3, Z = 4.
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