%0 Journal Article %1 OlbrichDeussner.1989b %A Olbrich-Deussner, Barbara %A Kaim, Wolfgang %A Gross-Lannert, Renate. %D 1989 %J Inorganic Chemistry %K bond;TCNE chromium complex complex;TCNQ complex;manganese complex;transition diimine ligand metal polycyano polynitrile property;cyanoquinone property;polynitrile transition %N 16 %P 3113--3120 %R 10.1021/ic00315a010 %T Electron-transfer catalyzed substitution in carbonyl complexes. Part 5. Electron-transfer autocatalytic formation, intramolecular charge transfer, and qualitatively different solvatochromism of s and p transition-metal carbonyl complexes with polynitrile ligands %V 28 %X Mononuclear transition metal carbonyl complexes (h1-TCNE)Cr(CO)2(C6Me6) and (h1-L)Mn(CO)2(h5-C5MenH5-n) with s (end-on) coordinated ligands L = TCNE, 2,5-dimethyl-7,8-dicyano-p-quinone diimine, TCNQ and the complexes (h2-TCNE or h2-TCNQ)M(CO)5 (M = Cr W) and (h2-fumarodinitrile)Mn(CO)2(h5-C5Me5) with a p (side-on) coordinated polycyano ligand have been studied by cyclic voltammetry (TCNE complexes) and electron absorption spectroscopy. Redn. potentials of the complexes were found above and below the values of free TCNE, indicating varying degrees of metal-to-ligand electron transfer in the ground state. This electron transfer is confirmed by vibrational spectroscopy and UV/visible/near-IR spectral response on C5R5 ligand modification. Solvent-induced dissocn. into the simultaneously ESR detectable paramagnetic metal fragment and the anion radical of the ligand was obsd. in one instance. Intense charge-transfer (MLCT/LMCT) transitions of the complexes occur in the visible and near-IR part of the spectrum. The p-coordinated complexes were found to exhibit a very different spectral response towards solvent variation than the s-bonded derivs. on SciFinder(R)

@article{OlbrichDeussner.1989b, abstract = {Mononuclear transition metal carbonyl complexes (\textgreek{h}1-TCNE)Cr(CO)2(C6Me6) and (\textgreek{h}1-L)Mn(CO)2(\textgreek{h}5-C5MenH5-n) with \textgreek{s} (end-on) coordinated ligands L = TCNE, 2,5-dimethyl-7,8-dicyano-p-quinone diimine, TCNQ and the complexes (\textgreek{h}2-TCNE or \textgreek{h}2-TCNQ)M(CO)5 (M = Cr W) and (\textgreek{h}2-fumarodinitrile)Mn(CO)2(\textgreek{h}5-C5Me5) with a \textgreek{p} (side-on) coordinated polycyano ligand have been studied by cyclic voltammetry (TCNE complexes) and electron absorption spectroscopy. Redn. potentials of the complexes were found above and below the values of free TCNE, indicating varying degrees of metal-to-ligand electron transfer in the ground state. This electron transfer is confirmed by vibrational spectroscopy and UV/visible/near-IR spectral response on C5R5 ligand modification. Solvent-induced dissocn. into the simultaneously ESR detectable paramagnetic metal fragment and the anion radical of the ligand was obsd. in one instance. Intense charge-transfer (MLCT/LMCT) transitions of the complexes occur in the visible and near-IR part of the spectrum. The \textgreek{p}-coordinated complexes were found to exhibit a very different spectral response towards solvent variation than the \textgreek{s}-bonded derivs. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Olbrich-Deussner, Barbara and Kaim, Wolfgang and Gross-Lannert, Renate.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/28519156db020003e74954c71489054c4/b_schwederski}, doi = {10.1021/ic00315a010}, interhash = {8dc9cb14364c3f5bb26ffbcb67bacf9a}, intrahash = {8519156db020003e74954c71489054c4}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {bond;TCNE chromium complex complex;TCNQ complex;manganese complex;transition diimine ligand metal polycyano polynitrile property;cyanoquinone property;polynitrile transition}, number = 16, pages = {3113--3120}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {Electron-transfer catalyzed substitution in carbonyl complexes. Part 5. Electron-transfer autocatalytic formation, intramolecular charge transfer, and qualitatively different solvatochromism of \textgreek{s} and \textgreek{p} transition-metal carbonyl complexes with polynitrile ligands}, volume = 28, year = 1989 }