Ligand and Tetrathiometalate Effects in Induced Internal Electron Transfer Reactions

New rhenium sulfide complexes, [Re(IV)(2)(&mgr;-S)(2)(&mgr;-S(2))(&mgr;-S(2)COR)(S(2)COR)(2)](-) and [Re(IV)(2)(&mgr;-S)(2)(S(2)COR)(4)], and a new tungsten sulfide complex, [WS(S(2))(S(2)CC(6)H(5))(2)], have been synthesized and isolated via induced internal redox reactions involving the appropriate tetrathiometalate and 1,1-dithiolate disulfide. The red complex [Re(IV)(2)(&mgr;-S)(2)(&mgr;-S(2))(&mgr;-S(2)COR)(S(2)COR)(2)](-), 1, was isolated from the reaction of dialkylxanthogen disulfide, [(ROCS(2))(2)], and tetraethylammonium tetrathioperrhenate, [Et(4)N][Re(VII)S(4)]. Crystal structure analysis of 1 reveals an edge-sharing (&mgr;-S)(2) bioctahedron containing both bridging disulfide and xanthate ligands. This reaction is compared to the known reaction between tetraalkylthiuram disulfide, [(R(2)NCS(2))(2)], and [Et(4)N][ReS(4)], which produces the green complex [Re(IV)(2)(&mgr;-S)(2)(S(2)CNR(2))(4)]. The corresponding green alkyl xanthate analogue, [Re(IV)(2)(&mgr;-S)(2)(S(2)COR)(4)], 2, was synthesized by a simple redox reaction between rhenium pentachloride, ReCl(5), and potassium alkyl xanthate, [K(S(2)COR)]. Comparing 1 with other known [ReS(4)](-)/1,1-dithiolate disulfide reaction products, such as [Re(IV)(2)(&mgr;-S)(2)(S(2)CNR(2))(4)] and [Re(III)(S(2)CC(6)H(5))(S(3)CC(6)H(5))(2)], shows a correlation between the electron-donating ability of the ligand and the nature of the reaction product. Reactions of [Et(4)N](2)[Mo(VI)S(4)], [Et(4)N][Re(VII)S(4)], or [Et(4)N](2)[W(VI)S(4)] with dithiobenzoate disulfide, [(S(2)CC(6)H(5))(2)], reveal a correlation between the ligand-to-metal charge transfer energy band (LMCT(1)) of the tetrathiometalate and the reaction product. The known purple complex [Mo(IV)(S(2)CC(6)H(5))(4)] and two new green complexes, [Re(III)(S(2)CC(6)H(5))(S(3)CC(6)H(5))(2)] (recently communicated) and [W(VI)S(S(2))(S(2)CC(6)H(5))(2)], were isolated from related reactions.