Reactivity of a Base-Stabilized Germanium(I) Dimer toward Group 9 Metal(I) Chloride and Dimanganese Decacarbonyl

The reactivity of the 2-imino-5,6-methylenedioxylphenylgermanium­(I) dimer toward group 9 metal­(I) chloride and dimanganese decacarbonyl is described. [LGe:]₂ (<b>1</b>, L = 2-imino-5,6-methylenedioxylphenyl) underwent a disproportionation reaction with 1.5 equiv of group 9 metal­(I) chloride [MCl­(cod)]₂ (M = Rh, Ir) in toluene to afford a mixture of the group 9 metallogermylene-chlorometal­(I) complexes [LGeμ-{M­(cod)}₂Cl] (M = Rh (<b>2</b>), Ir (<b>4</b>)) and chlorogermylene-chlorometal­(I) complexes [L­(Cl)­GeM­(cod)­Cl] (M = Rh (<b>3</b>), Ir (<b>5</b>)), respectively. The disproportionation property of <b>1</b> is further evidenced by its reaction with 0.5 equiv of Mn₂(CO)₁₀ in refluxing toluene to form a mixture of the manganogermylene dimer [(LGe)­μ-{Mn­(CO)₄}]₂ (<b>7</b>) and free ligand [LH] (<b>8</b>). Compounds <b>2</b>–<b>5</b>, <b>7</b>, and <b>8</b> were elucidated by NMR spectroscopy, X-ray crystallography, and DFT calculations, respectively