Mono- and binuclear tri- and tetracarbonyl complexes of chromium(0), molybdenum(0), and tungsten(0) with the 2,2'-bipyrimidine radical anion

. Inorganic Chemistry 23 (21): 3365--3368 (1984)


((CO)4M)x bpym-. (x = 1, 2; M = Cr, Mo, W; bpym = 2,2'-bipyrimidine) were studied by high-resoln. ESR. The unpaired electron resides predominantly in the LUMO of the heterocycle; HMO-McLachlan calcns. were used to interpret the hyperfine coupling consts. ((CO)4Mo)2bpym- underwent successive replacement of 2 axial CO groups by PBu3. A p*/s* hyperconjugation model accounted for the facile CO substitution and for the spin transfer to the peripheral 31P nuclei. An unexpected behavior was found for the g values of the complexes, which were generally lower than the g of the free ligand. This result points to a strong contribution from a low-lying electronically excited state to the radical ground state. on SciFinder(R)

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