((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)
%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 = {2019-07-15T13:41:23.000+0200},
author = {Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e66e3f6c255933e8a07cff4565c504df/b_schwederski},
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 = {2019-07-15T11:42:10.000+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
}
