Abstract
The title salts formula Rh(Me 2NCS 2(RNC) 2(TCNQ) and Rh(EtO) 2PS 2(RNC) 2(TCNQ) (R = Ph, 4-MeC 6H 4, and 4-MeOC 6H 4 were prepared. The binding energies pf Rh 3d 3 2 and 3d 5 2 electrons obtained from X-ray photoelectron spectra of these salts fall between those of Rh IL(RNC) 2 and Rh IIIL(RNC) 2I 2, and are almost the same as those of the TCNE salts, RhL(RNC) 2(TCNE) (L = Me 2NCS 2 and (EtO) 2PS 2. These results, in addition to electronic absorption and ESR spectra, suggest that the TCNQ salts involve the Rh(II) species and the TCNQ ⨪ radical anion and that the Rh(II) species exist as dimes with the Rh(II)Rh(II) bonding in the solid state. All the TCNQ salts behave as the semi-conductors in the 202̄90°C range, although the electrical resistivities are large (10 7–10 11 Ω cm at 298 K as compacted samples).
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