Bimetallic Group 6 Tricarbonyls Triply-Bridged by Bis(phenylthio)alkane Bidentate Ligands

Reactions of the labile complex (Me3tach)M(CO)3 (Me3tach = 1,3,5-trimethyl-1,3,5-triazacyclohexane; M = W, Mo) with bis(phenylthio)alkanes ( = PhS(CH2)nSPh), (2:3 molar ratio) in CH2Cl2 as solvent (at 35 oC M = W, 0 oC M = Mo) afforded in good yields bimetallic tricarbonyl complexes triply- bridged by bis(phenylthio)alkanes of the type [M(CO)3]2(μ-PhS-(CH2)n-SPh)3 [n = 3 (a), 4 (b), 5 (c), 6 (d); M = W (1), Mo (2)]. These new triply-bridged complexes were characterized by 1H NMR, FT-IR and elemental analysis. Additionally, it has been observed that the thermodynamic stability of some of these new complexes in chlorinated hydrocarbons depends mainly on the nature of the metal center and varies in the order W >> Mo.