The carbonyl compounds, TpRMo(NO)(L)(CO) where TpR = tris(pyrazolyl)borate (Tp) or tris(3,5-dimethylpyrazolyl)borate (Tp*), and L = 1-methylimidazole (1-MeIm), 4-dimethylaminopyridine (DMAP), PMe3, pyridine, 3-chloropyridine, P(p-tolyl)3, PPh3, or P(OMe)3 have been prepared from the dicarbonyl complex TpRMo(NO)(CO)2 by thermal displacement of CO. An N-heterocyclic carbene complex has also been prepared where L = 1,3-dimethylimidazol-2-ylidene (NHC) using 1,3-dimethylimidazolium-2-carboxylate. Oxidation of these TpRMo(NO)(L)(CO) complexes by cumene hydroperoxide, t-butyl hydroperoxide, or O2 gives η2-carbon dioxide complexes, TpRMo(NO)(L)(η2-CO2), for L = 1-MeIm, DMAP, PMe3, NHC, pyridine, or 3-chloropyridine. These complexes have been characterized by X-ray crystallography, IR and NMR spectroscopy. The η2-CO2 complexes are air stable and are thermally stable in solution at room temperature. Reduction of TpRMo(NO)(L)(η2-CO2) back to TpRMo(NO)(L)(CO) can be accomplished using chemical reductants.

Synthesis of molybdenum carbon dioxide complexes via oxidation of a carbonyl ligand

249th National Meeting (2015)

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