摘要
The S-S bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO) 5 ] - gives rise to an extensive chemistry. Oxidative decarbonylation addition of 2,2′-dithiobis(pyridine-N-oxide) to [Mn(CO) 5 ] - , followed by chelation and metal-center oxidation, led to the formation of [Mn II (-SC 5 H 4 NO-) 3 ] - (1). The effective magnetic moment in solid state by SQUID magnetometer was 5.88 μ B for complex 1, which is consistent with the Mn II having a high-spin d 5 electronic configuration in an octahedral ligand field. The average Mn(II)-S, S-C and N-O bond lengths of 2.581(1), 1.692(4) and 1.326(4) Å, respectively, indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC 5 H 4 NO] - ligand in complex 1 is mainly localized on the oxygen atom. The results are consistent with thiolate-donor [-SC 5 H 4 NO] - stabilization of the lower oxidation state of manganese (Mn(I)), while the O,S-chelating [-SC 5 H 4 NO-] - ligand enhances the stability of manganese in the higher oxidation state (Mn(II)). Activation of S-S bond as well as O-H bond of 2,2′-dithiosalicylic acid by [Mn(CO) 5 ] - yielded [(CO) 3 Mn(μ-SC 6 H 4 -C(O)-O-) 2 Mn (CO) 3 ] 2- (4). Oxidative addition of bis(o-benzamidophenyl) disulfide to [Mn(CO) 5 ] - resulted in the formation of cis-[Mn(CO) 4 (SR) 2 ] - (R=C 6 H 4 NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear [(CO) 3 Mn(μ-SR) 3 Co(μ-SR) 3 Mn(CO) 3 ] - (8) possessing a homoleptic hexathiolatocobalt(III) core. © 2002 Published by Elsevier Science B.V.