Abstract
95Mo NMR chemical shifts are reported for a range of molybdenum(0) carbonylate anions of the type [Mo(CO) 5X] − (X = halide or pseudohalide). The dimethylsulphoxide solution data substantiate the existence of more than one product, unexpected products and ambidentate pseudohalogen bonding modes. The sensitivity of the 95Mo NMR chemical shifts to the ligand field and polarizability properties of the anions in the [Mo(CO) 5X] − complexes results in an over 500 ppm range of values (−1980 to −1435 ppm); the shielding order is H − > CN − > I − > NCO − > NCS − > NCSe − > Br − > N − 3 > NO − 2 > Cl − > O 2CH − > O 2N − > OCH − 3. Species arising from the reaction of Mo(CO) 6 with hydroxide ion have been previously implicated in the homogeneous catalysis of the water-gas shift reaction; the utility of 95Mo NMR spectroscopy in identifying some of these products is also described.
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