cis-Mo(CO)2(PBu3)2(bdz) (bdz = 3,3'-bipyridazine, 2,2'-bipyrazine, 2,2'- and 4,4'-bipyrimidine) were prepd. They can undergo reversible 1-electron oxidn. and redn. and show small redox potential differences \textless1.5 V. The small HOMO-LUMO gap gives rise to long-wavelength metal-to-ligand charge transfer absorptions, an assignment which is supported by ESR studies. Guidelines for the construction of complexes with small charge-transfer absorption energies by CO/PR3 exchange are presented. Although a ligand-centered MO is occupied during redn., the small g factors of the radical complexes indicate low-lying ligand-field-excited states which are believed to be responsible for the pronounced light-sensitivity of the compds. cis-Mo(CO)2(PBu3)2(bdz) were also characterized by IR and 1H NMR spectral methods. on SciFinder(R)
%0 Journal Article
%1 Ernst.1988b
%A Ernst, Sylvia
%A Kohlmann, Stephan
%A Kaim, Wolfgang.
%D 1988
%J Journal of Organometallic Chemistry
%K bidiazine bipyrazine carbonyl complex complex;electrochem complex;molybdenum molybdenum phosphine;bipyridazine phosphine;bipyrimidine phosphine;charge phosphine;photosensitivity redox transfer
%N 2
%P 177--192
%T cis-Bis(tributylphosphine)molybdenum dicarbonyl complexes with four isomeric bidiazine ligands
%V 354
%X cis-Mo(CO)2(PBu3)2(bdz) (bdz = 3,3'-bipyridazine, 2,2'-bipyrazine, 2,2'- and 4,4'-bipyrimidine) were prepd. They can undergo reversible 1-electron oxidn. and redn. and show small redox potential differences \textless1.5 V. The small HOMO-LUMO gap gives rise to long-wavelength metal-to-ligand charge transfer absorptions, an assignment which is supported by ESR studies. Guidelines for the construction of complexes with small charge-transfer absorption energies by CO/PR3 exchange are presented. Although a ligand-centered MO is occupied during redn., the small g factors of the radical complexes indicate low-lying ligand-field-excited states which are believed to be responsible for the pronounced light-sensitivity of the compds. cis-Mo(CO)2(PBu3)2(bdz) were also characterized by IR and 1H NMR spectral methods. on SciFinder(R)
@article{Ernst.1988b,
abstract = {cis-Mo(CO)2(PBu3)2(bdz) (bdz = 3,3'-bipyridazine, 2,2'-bipyrazine, 2,2'- and 4,4'-bipyrimidine) were prepd. They can undergo reversible 1-electron oxidn. and redn. and show small redox potential differences {\textless}1.5 V. The small HOMO-LUMO gap gives rise to long-wavelength metal-to-ligand charge transfer absorptions, an assignment which is supported by ESR studies. Guidelines for the construction of complexes with small charge-transfer absorption energies by CO/PR3 exchange are presented. Although a ligand-centered MO is occupied during redn., the small g factors of the radical complexes indicate low-lying ligand-field-excited states which are believed to be responsible for the pronounced light-sensitivity of the compds. cis-Mo(CO)2(PBu3)2(bdz) were also characterized by IR and 1H NMR spectral methods. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Ernst, Sylvia and Kohlmann, Stephan and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b6a49182236dc1aac21334202b2e3c38/b_schwederski},
interhash = {41a1f335298e2f5d973b4202db7a9386},
intrahash = {b6a49182236dc1aac21334202b2e3c38},
journal = {Journal of Organometallic Chemistry},
keywords = {bidiazine bipyrazine carbonyl complex complex;electrochem complex;molybdenum molybdenum phosphine;bipyridazine phosphine;bipyrimidine phosphine;charge phosphine;photosensitivity redox transfer},
number = 2,
pages = {177--192},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {cis-Bis(tributylphosphine)molybdenum dicarbonyl complexes with four isomeric bidiazine ligands},
volume = 354,
year = 1988
}
