Electronic Communication in Dinuclear C4-Bridged Tungsten Complexes

Abstract

The dinuclear tungsten carbyne [X(CO)(2)(dppe)WC(4)W(dppe)(CO)(2)X] (dppe = 1,2-bis(diphenylphosphino)ethane; X = I (3), Cl (7)) complexes were prepared from the bisacetylide precursor Li(2)[(CO)(3)(dppe)WC(4)W(CO)(3)(dppe)] (2) via oxidative replacement of one CO group at each tungsten center with a halide substituent. The iodide ligand in 3 could be substituted with isothiocyanate or triflate resulting in [X(CO)(2)(dppe)WC(4)W(dppe)(CO)(2)X] complexes (X = NCS (8), OTf (9)). Substitution of two and all four CO ligands in 3 was achieved via subsequent photolytic or thermal activation with dppe. The "half-substituted" complex [I(CO)(2)(dppe)WC(4)W(dppe)(2)I] (11) allows reversible one-electron oxidation which results in the monocationic species [I(CO)(2)(dppe)WC(4)W(dppe)(2)I][PF(6)] (11[PF(6)]). The "all-dppe substituted" complex [I(dppe)(2)WC(4)W(dppe)(2)I] (10) possesses two reversible redox states leading to the stable monocationic [I(dppe)(2)WC(4)W(dppe)(2)I][PF(6)] (10[PF(6)]) and the dicationic [I(dppe)(2)WC(4)W(dppe)(2)I][PF(6)](2) (10[PF(6)](2)) compounds. The complexes 2, 3, [W(CO)(3)(dppe)(C[triple bond]CPh)(I)] (4), [X(CO)(2)(dppe)W[triple bond]C-C(Me)=C(Me)-C[triple bond]W(dppe)(CO)(2)X] (X = I (5), Cl (6)), 7, 8, 10, 11 and 11[PF(6)] were characterized by single crystal X-ray diffraction. The electronic properties of complexes 10, 10[PF(6)], 10[PF(6)](2), as well as of compounds 11 and 11[PF(6)], were investigated using cyclic voltammetry (CV), EPR, IR, near-IR spectroscopy, and magnetization measurements. These studies showed that the [W][triple bond]C-C[triple bond]C-C[triple bond][W] canonical form of the bridged system with strong tungsten-carbon interaction contributes significantly to the electronic coupling in the mixed-valent species 10[PF(6)] (comproportionation constant K(c) = 7.5 x 10(4)) and to the strong antiferromagnetic coupling in the dicationic complex 10[PF(6)](2) (exchange integral J = -167 cm(-1)). In addition, the rate for electron transfer between the tungsten centers in 10[PF(6)] was evaluated by near-IR and IR studies.