Reactions of Dithiolate Ligands in Mononuclear Complexes of Rhenium(V). 2. Cp‘ ‘ReCl<sub>2</sub>(η<sup>2</sup>-SC<sub>3</sub>H<sub>6</sub>S) and Related Derivatives
作者:J. A. Kanney、B. R. Jagirdar、B. C. Noll、M. Rakowski DuBois
DOI:10.1021/om020626t
日期:2003.1.1
The syntheses and characterizations of Cp"ReCl2(SC3H6S), 1, Cp"ReCl3(SCHMe2), 2, and Cp"ReCl2(SCHMe2)(2), 3, are reported (Cp" = C5Me4Et). Complex 2 has been characterized by an X-ray diffraction study, which confirms its mononuclear structure. Reactions of 1, 2, and 3 have been studied and compared with those characterized previously for Cp"ReCl2(SC2H4S). For example, the thermal reaction of 1 in toluene at 100 degreesC, results in the elimination of HCl and formation of a complex with a chelated thiolate/thialdehyde ligand, Cp"ReCl(SCH2CH2CH=S), 5. Complex 5 can also be synthesized at a lower temperature by the reaction of 1 with excess triethylamine. Spectroscopic characteristics and reactivity of 5 are reported.
Syntheses of a Cp‘ReS Derivative and More Complex Products
作者:S. H. Pawlicki、B. C. Noll、J. A. Kanney、M. Rakowski DuBois
DOI:10.1021/ic0206241
日期:2003.3.1
The reaction of Cp'ReCl2S3 (CP' = Me4EtC5) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-S)](2), 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl2(SC2H4S) with (Me3Si)(2)S resulted in the formation of three new products: Cp'ReS(SC2H4S), 4; Cp'Re(S-3)(SC2H4S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S) (mu,eta(2)-SC2H4S)(mu,eta(1)-SC2H4S](2)Cl-2, 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues.