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Issue 14, 2003
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Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

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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(μ-TCNQ), 1, and [Re2Cl4(dppm)2]2(μ-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(μ-TCNQ)·10THF revealed the presence of a trans2 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(μ-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 χTIP values of 7.29 × 10−3 and 6.23 × 10−3 emu mol−1, respectively.

Graphical abstract: Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

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Article information


Submitted
24 Apr 2003
Accepted
22 May 2003
First published
12 Jun 2003

Dalton Trans., 2003, 2937-2944
Article type
Paper

Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

S. L. Bartley, M. J. B. Jr., R. Clérac, H. Zhao, X. Ouyang and K. R. Dunbar, Dalton Trans., 2003, 2937
DOI: 10.1039/B304509A

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