%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 = {2022-06-15T11:26:56.000+0200}, author = {Ernst, Sylvia and Kohlmann, Stephan and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b6a49182236dc1aac21334202b2e3c38/huebleriac}, 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 = {2022-06-15T09:26:56.000+0200}, title = {cis-Bis(tributylphosphine)molybdenum dicarbonyl complexes with four isomeric bidiazine ligands}, volume = 354, year = 1988 }