Ruthenium complexes with N(SPR2)(2)(-) (R = Ph or Pr-i)

Reactions of [Ru(PPh3)(3)Cl-2], [Ru(CO)(2)Cl-2](x), or [Ru(dmso)(4)Cl-2] (dmso=dimethyl sulfoxide) with KLR [L-R=N(SPR2)(2), R=Ph or Pr-i] afforded [Ru(L-R)(2)(PPh3)] (R=Ph 1 or Pr-i 2), cis-[Ru(L-R)(2)(CO)(2)] (L=Ph 3 or Pr-i 4), or cis-[Ru(L-Ph)(2)(dmso)(2)] 5, respectively. The crystal structures of complexes 1 and 2 have been determined. They show weak agostic interaction between Ru and L-R with calculated Ru ... H-C separations of 3.37 and 2.91 Angstrom, respectively. The Ru-P and average Ru-S distances in 1 are 2.218(1) and 2.400 Angstrom, respectively. The corresponding bond lengths for 2 are 2.210(2) and 2.404 Angstrom. Treatment of 2 with (BuNC)-N-t afforded trans-[Ru(L-Pr)(2)((BuNC)-N-t)(2)] 6, the average Ru-S and Ru-C distances of which are 2.453 and 1.990(3) Angstrom, respectively. Reaction of RuCl3 with KLR in methanol gave the homoleptic complexes [Ru(L-R)(3)] (L=Ph 7 or Pr-i 8). The average Ru-S distance and S-Ru-S angle in 7 are 2.414 Angstrom and 97.41 degrees, respectively. While complex 1 reacts with pyridine (py) to give [Ru(L-Ph)(2)(PPh3)(py)] 9, reaction of 2 with py led to isolation of structurally characterised [Ru(L-Pr)(2)(SO)] 10. The Ru-S(O) and S-O bond lengths in 10 are 2.0563(11) and 1.447(3) Angstrom, respectively, the Ru-S-O angle being 125.5(2)degrees. Treatment of 1 with SO2 afforded structurally characterised cis-[Ru(L-Ph)(2)(PPh3)(SO2)] 11. The SO2 ligand binds to Ru in 11 in a eta(1)-S mode and the Ru-S(O) distance is 2.140(4) Angstrom. Complex 2 reacted with SO2 to give the mu-sulfato-bridged ruthenium(III) dimer [{Ru(L-Pr)(PPh3)}(2)(mu-SO4)(2)] 12, which has been characterised by X-ray crystallography. The Ru-P and average Ru-S and Ru-O distances in 12 are 2.294(2), 2.321 and 2.133 Angstrom, respectively. Complex 1 is capable of catalysing hydrogenation of styrene in the presence of Et3N presumably via a ruthenium hydride intermediate