Synthesis and Structural Characterization of [Cu(DMF)_6][(η~5-C_5Me_5)WS_3(CuBr)_3]_2·Et_2O

1 INTRODUCTION In the last decade, we have been interested in the synthesis of PPh4](h5-C5Me5)MS3] (M = Mo, W)1, 2] , Whose organometallic trisulfido anions show high reactivity towards various transition metals3~6] . We once reported that the reaction of PPh4](h5-C5Me5)WS3] with CuBr in CH3CN afforded a double incomplete-cubane cluster PPh4]2(h5-C5Me5)WS3(CuBr)3]23], while the analogous reaction of PPh4](h5-C5Me5)WS3] with CuBr in CHCl3 gave rise to a 揻our-…

Synthesis and Structural Characterization of [Cu(DMF)6][(η5-C5Me5)WS3(CuBr)3]2·Et2O

The reactions of PPh4](η5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt Cu(DMF)6](η5-C5Me5)WS3(CuBr)3]2·Et2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) A, V = 7054.6(8) A3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, μ (Mo Kα) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0σ(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one (η5-C5Me5)WS3(CuBr)3]22-dianion, one Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (η5-C5Me5)WS3(CuBr)3 fragments connected by a pair of Cu-Br-Cu bridges to form a double incomplete-cubane structure. The range of W-Cu distance is 2.657(1)~2.677(2) A in the W2Cu6S6 cluster core.