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