Structural, electronic and magnetic properties of metalmetal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands Academic Article uri icon

abstract

  • The syntheses, spectroscopic properties, redox chemistry, and solid-state structures of products obtained from the reaction of Re2Cl4(dppm)2 (dppm = bis(diphenylphosphino) methane) with the polycyano acceptors TCNQ (7,7,8,8-tetracyanoquinodimethanido) and DM-DCNQI (2,5-dimethyl-N, N-dicyanoquinonediimine) are described. The compounds [Re2Cl4(dppm)2]2(-TCNQ), 1, and [Re2Cl4(dppm)2]2(-DM-DCNQI), 2, have been prepared by reaction of two equivalents of Re2Cl4(dppm)2 with TCNQ and DMDCNQI, respectively, in THF or CH2Cl2. A single-crystal X-ray crystallographic study of [Re2Cl4(dppm)2]2(-TCNQ)10THF revealed the presence of a trans-2 bidentate mode for the bridging TCNQ ligand that joins two Re2Cl4(dppm)2 molecules through equatorial positions. In a similar fashion, the compound [Re2Cl4(dppm)2]2(-DM-DCNQI)10THF consists of two Re2 units coordinated to the two nitrile positions of the DM-DCNQI ligand. The electronic properties of both compounds are unusual in that they exhibit intense, broad absorptions that span the near-IR region and extend into the mid-IR. The electrochemistry of the compounds consists of numerous oxidation and reduction processes in the range of +2.0 to 2.0 V as determined by cyclic voltammetry. Both 1 and 2 exhibit temperature independent paramagnetism (TIP) with large TIP values of 7.29 103 and 6.23 103 emu mol1, respectively. 2003 The Royal Society of Chemistry.

published proceedings

  • Dalton Trans.

author list (cited authors)

  • Bartley, S. L., Jr., M., Clrac, R., Zhao, H., Ouyang, X., & Dunbar, K. R.

citation count

  • 17

complete list of authors

  • Bartley, Stuart L||Jr., Mervin J Bazile||ClĂ©rac, Rodolphe||Zhao, Hanhua||Ouyang, Xiang||Dunbar, Kim R

publication date

  • January 2003