HYDRIDO THIOLATO AND THIOLATO COMPLEXES OF RUTHENIUM(II) CARBONYL PHOSPHINES

Oxidative addition of RSH (R = H, alkyl, aryl) or RSSR (R = aryl) to Ru(CO)2L3 (L = PPh3, 1) yields respectively cct-RuH(SR)(CO)2L2 (type 2) (cct = cis,cis,trans) or cct-Ru(SR)2(CO)2L2 (type 3); a hydrido selenolate species is made similarly using PhSeH. Methods for in situ formation of corresponding mixed bis(thiolate) species are also given. 1 is generally unreactive toward thioethers, although with propylene sulfide cct-Ru(eta-2-S2) (CO)2L2 is produced. Metathesis reactions of cct-RuCl2(CO)2L2 with NaSR salts yield 3 (R = aryl) or, when R = Et, cct-RuCl(SEt)(CO)2L2 or [L(CO)2Ru(mu-2-SEt)2(mu-3-SEt)Na(THF)]2 (4), depending on reaction conditions. The complexes are characterized by IR spectroscopy, H-1, P-31, and, in some cases, C-13 NMR spectroscopy, and for 2g and 3g (R = SC6H4pMe) and 4, X-ray crystallography. All three complexes crystallized in the space group P1BAR. For 2g, a = 12.340 (4) angstrom, b = 14.948 (3) angstrom, c = 10.684 (4) angstrom, alpha = 90.05 (3)-degrees, beta = 99.27 (3)-degrees, gamma = 86.84 (3)-degrees, V = 1942 (1) angstrom 3, and Z = 2; the structure refined to R = 0.032 and R(w) = 0.037 for 7174 reflections with F(o)2 > 3-sigma(F(o)2). Corresponding crystallographic data for 3g are a = 13.173 (3) angstrom, b = 19.766 (4) angstrom, c = 9.770 (4) angstrom, c = 9.770 (4) angstrom, alpha = 98.26 (2)-degrees, beta = 91.24 (3)-degrees, gamma = 78.31 (2)-degrees, V = 2465 (1) angstrom 3, Z = 2, R = 0.041, and R(w) = 0.043 for 3597 reflections; for 4, a = 12.189 (3) angstrom, b = 13.124 (3) angstrom, c = 12.032 (4) angstrom, alpha = 99.70 (2)-degrees, beta = 110.61 (2)-degrees, gamma = 67.95 (2)-degrees, V = 1668.4 (8) angstrom 3, Z = 1, R = 0.039, and R(w) = 0.043 for 4252 reflections. 4 has an unprecedented network of transition-metal and alkali-metal ions bridged by thiolate ligands: four thiolates bridge one Ru and one Na, and two thiolates bridge one Ru and two Na atoms. The geometries at Ru and Na are close to octahedral and square pyramidal, respectively. Trends are noted for the H-1 NMR shifts and 2J(PH) values for the hydride in 2, and an additivity rule formulated for the P-31 shift within the cct-Ru(SR)(SR')(CO)2(PPh3)2 species. Limited kinetic data suggest that the oxidative addition reactions to 1 probably proceed via a nonradical process, following dissociation of a PPh3 ligand.