Trithiotungsten(VI) complexes having phosphine-thiolate hybrid ligands: synthesis and cluster forming reactions with CuBr, FeCl(2), and [Fe(CH(3)CN)(6)](ClO(4))(2)

Five-coordinated trithiotungsten complexes (PPh(4))(dmsp)W(S)(3)] (1a) and (PPh(4))(dpsp)W(S)(3)] (1b) (R(2)PCH(2)CH(2)S(-); R = Me (dmsp-)), Ph (dpsp-))) were synthesized by addition of Hdmsp and Hdpsp to a THF solution of (PPh(4))(EtS)W(S)(3)]. Treatment of 1a with CuBr in the presence of PPh(3) in CH(3)CN afforded a WCu(2) cluster (dmsp)WS(3)Cu(2)(PPh(3))(2)Br (2). The reaction of 1a with 1 equiv of FeCl(2) went smoothly to generate a 1:1 adduct (PPh(4))(dmsp)WS(3)(FeCl(2))] (3), while 3 did not react further with excess FeCl(2). On the other hand, 3 was found to react with Fe(CH(3)CN)(6)](ClO(4))(2), giving rise to an unusual tetranuclear cluster, (dmsp)WS(3)](2)Fe(2)Cl (4), while the reaction of 1a with 2 equiv of Fe(CH(3)CN)(6)](ClO(4))(2) led to a cyclic octanuclear cluster (dmsp)WS(3)Fe](4) (5). Although the oxidation states of W(VI), Cu(I), and Fe(II) are retained in 2 and 3, reduction of the metal ions occurs in the formation of 4 and 5. All the complexes reported in this paper were structurally characterized by X-ray analysis. It is anticipated that the new type of trithiotungsten complexes, 1a and 1b, will serve as potential synthons for various heterometallic sulfide clusters.