The Synthesis of 1,1'-Bicobaltocene Salts of Tetracyano-P-Quinodimethanide and the Sturcture of 1,1'-Bicobaltocene (Co (III) Co (III)) (TCNQ)3

摘要

The reaction of 1,1'-bicobaltocene(Co(III)Co(III))(PF6)2 or the analogous mixed valence compound (Co(III)Co(II) with excess ((C2H5)3NH) (TCNQ2 and TCNQ yields the complex salt 1,1'-bicobaltocene(Co(III)Co(III))(TCNQ)3. The complex salt crystallizes in the triclinic system, space group P1 with unit cell dimensions a = 7.475(4), b = 10,113(5), and c = 14.306(3) A, and alpha = 92.51(3) deg, beta = 98.84(3) deg and gamma = 92.64(4) deg. The conventional and weighted R factors for 1979 reflections for which I was greater than 3o-(I) are R = 0.047 and Rw = 0.044. The TCNQ units stack to form an alternating chain with two short, adjacent interplanar spacings of 3.15 A, followed by a longer interplanar spacing of 3.45 A. The interplanar spacing of the fulvalence moities in the cation is 3.270 A, and the cobalt-carbon bond distances range from 2.012(5) to 2.041(5)A. The complex salt is diamagnetic and the electrical conductivity of a pressed pellet sample is 0.03 ohm/cm. (Author)