%0 Journal Article %1 Kaim.1984h %A Kaim, Wolfgang. %D 1984 %J Inorganic Chemistry %K Group VIB anion;molybdenum bipyrimidine carbonyl carbonyl;ESR radical substitution tributylphosphine %N 21 %P 3365--3368 %R 10.1021/ic00189a019 %T Mono- and binuclear tri- and tetracarbonyl complexes of chromium(0), molybdenum(0), and tungsten(0) with the 2,2'-bipyrimidine radical anion %V 23 %X [((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)]

@article{Kaim.1984h, abstract = {[((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 \textgreek{p}*/\textgreek{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)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e66e3f6c255933e8a07cff4565c504df/huebleriac}, doi = {10.1021/ic00189a019}, interhash = {89d779412465b6d16be7335a534843e7}, intrahash = {e66e3f6c255933e8a07cff4565c504df}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {Group VIB anion;molybdenum bipyrimidine carbonyl carbonyl;ESR radical substitution tributylphosphine}, number = 21, pages = {3365--3368}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Mono- and binuclear tri- and tetracarbonyl complexes of chromium(0), molybdenum(0), and tungsten(0) with the 2,2'-bipyrimidine radical anion}, volume = 23, year = 1984 }