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Published on: May 26, 2019
Synthesis and reactivity of catecholate complexes containing quadruply bonded metal ions
Jason Christ1, Corinne Epps, Victoria Pritchard
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
Abstract:
Quadruply bonded metal complexes of rhenium and molybdenum have been prepared with tetrachlorocatechol. Structural characterization on the [Re(2)(Cl(4)Cat)(4)](2-) anion has shown that it consists of distorted square-planar Re(Cl(4)Cat)(2) units linked by a short (2.2067 A) quadruple Re-Re bond. The addition of tetrachlorocatechol to molybdenum acetate was used to prepare the isoelectronic molybdenum analogue "[Mo(2)(Cl(4)Cat)(4)](4-)". This complex was found to be far more reactive than the rhenium dimer. A dimer containing a Mo-Mo double bond, [(Cl(4)Cat)(2)Mo(mu-O)(mu-OCH(3))Mo(Cl(4)Cat)(2)](3-), was obtained as the methanolysis product of the complex formed initially, and the oxomolybdenum(V) monomer [MoO(Cl(4)Cat)(2)](-) was formed under more oxidative conditions. Both complexes are oxygen-sensitive, giving [MoO(2)(Cl(4)Cat)(2)](2-) as the final air-stable complex product.
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