Abstract
Abstract The equilibria of Cr(II) with formate ion in aqueous media have been analyzed by spectrophotometric and nuclear magnetic resonance techniques. A binuclear complex is observed to be incompletely formed throughout the intermediate formate ion concentration range and is suggested to be structually analogous to the quadruply metal-metal bonded dichromium tetraacetate. This complex is formed via the equilibrium 2 Cr(Formate)+ + Formate− Cr2 (Formate)3 + for which the equilibrium constant is 2.1 ± 0.2 M−2. At the highest formate ion concentrations studied, the binuclear complex dissociates to mononuclear high-spin complexes with formate to metal ion ratios greater than 3. The existence of the binuclear complex in only a narrow ligand concentration range suggests that the chromium-chromium bond is of marginal importance to the stability of the binuclear species and is subordinate to chromium(II)-formate ion bond strength.
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