FORMATION OF SULFIDE NIOBIUM COMPLEXES THROUGH C-S BOND ACTIVATION

Upon reacting (eta(5)-C5H5)(2)NbCl2, eta(5)-C5H5 = CP, and (Ph)(3)Sn(S Ph), in THF, (eta(5)- C5H5)(2)Nb(Cl)(mu-S)Sn(Ph)(3)(Cl), 1, and (eta(5 )-C5H5)(2)Nb(S)Cl, 2, were obtained. Complexes 1 and 2 were characteri zed by IR, H-1-NMR, C-13-NMR, Mossbauer spectroscopies, elemental anal ysis as well as by atomic absorption. Hydrolysis of 1 yielded the mu-o xo species, (eta(5)-C5H5)(2)Nb(Cl)(mu-O)Sn(Ph)(3)Cl, 3, which was char acterized by IR, H-1-NMR, C-13-NMR and Mossbauer spectroscopies, eleme ntal analysis, atomic absorption as well as by X-ray crystallography. It crystallizes in the space group Pca2(1) with a = 17.282(3), b = 18. 122(4), c = 17.3269(2), V = 5426.2(16) Angstrom(3), and Z = 8. Additio nal studies indicated that the complexes were formed as a result of th e nucleophilic displacement of the niobium-chloride bond by the thiola te ligand followed by a C-S bond cleavage. The cleavage occurs with an excess of the thiolate compound equal to or greater than 2:1.