Syntheses of 1,1'-Bicobaltocene Salts of Tetracyano-P-Quinodimethane, Tetrabromoquinone, and Tetrabromodiphenoquinone: and the Structure of 1,1'-Bicobaltocene Co(III)Co(III)(TCNQ)3

摘要

The reaction of 1,1'-bicobaltocene(Co(III)Co(III)-(PF6)2, (BFDCo(III,III)(PF6)2, or the analogous mixed valence compound (Co(III)Co(II)) with excess ((C2H5)3NH)(TCNQ)2 and TCNQ yields the complex salt 1,1'-bicobaltocene(Co(III)Co(III)((TCNQ)3. Reaction of (BFDCo(III,III))(PF6)2 with excess tetrabromoquinone (bromanil, BA) and its sodium salt produces (BFD-Co(III,III))(BA)3, while reaction with tetrabromodiphenoquinone (TBDQ) yields (BFDCo(III,III))(TBDQ)3. The TCNQ units in the complex salt (BFDCo(III,III))(TCNQ)3 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 fulvalene moieties 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 salts are diamagnetic, and the electrical conductivities of pressed pellet samples range from .03 to .0003/ohm/cm. (Author)