%0 Journal Article %1 Stufkens.1991 %A Stufkens, Derk J. %A Snoeck, Theo L. %A Kaim, Wolfgang %A Roth, Thomas %A Olbrich-Deussner, Barbara. %D 1991 %J Journal of Organometallic Chemistry %K Raman Raman;charge Raman;chromium Raman;hybridization Raman;tungsten carbonyl carbonyltetracyanoethane charge chromium complex metal tetracyanoethane transfer transfer;cyanoethane tungsten %N 1-2 %P 189--195 %R 10.1016/0022-328X(91)86144-F %T Resonance Raman study of (h2-TCNE)M(CO)5 (M = Cr, W; TCNE = tetracyanoethene). Evidence for an olefin-complex $\rightarrow$ metallacyclopropane transition upon low-energy metal-to-ligand charge-transfer excitation %V 409 %X A solid state resonance Raman investigation of the nonhydrogen-contg. title complexes was performed with long-wavelength laser excitation (514.5-611 nm). The spectra confirmed the h2-coordination of the p-acceptor olefin tetracyanoethene (TCNE) and showed that the absorption bands near 700 nm arise from transitions between the metal and TCNE. The metal-to-ligand charge-transfer (MLCT) character of these transitions is much more pronounced for the tungsten complex. These observations confirm the higher degree of metal (d)/ligand(p*) orbital mixing in the chromium complex and also provide evidence for a structural change from that of an alkene p-complex towards a metallacyclopropane arrangement upon MLCT excitation. on SciFinder(R)

@article{Stufkens.1991, abstract = {A solid state resonance Raman investigation of the nonhydrogen-contg. title complexes was performed with long-wavelength laser excitation (514.5-611 nm). The spectra confirmed the \textgreek{h}2-coordination of the \textgreek{p}-acceptor olefin tetracyanoethene (TCNE) and showed that the absorption bands near 700 nm arise from transitions between the metal and TCNE. The metal-to-ligand charge-transfer (MLCT) character of these transitions is much more pronounced for the tungsten complex. These observations confirm the higher degree of metal (d)/ligand(\textgreek{p}*) orbital mixing in the chromium complex and also provide evidence for a structural change from that of an alkene \textgreek{p}-complex towards a metallacyclopropane arrangement upon MLCT excitation. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Stufkens, Derk J. and Snoeck, Theo L. and Kaim, Wolfgang and Roth, Thomas and Olbrich-Deussner, Barbara.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/22539e4acde94eda78c7e5aa821bf1bd5/huebleriac}, doi = {10.1016/0022-328X(91)86144-F}, interhash = {311dc8f36c9d8b65de73ad17328135d2}, intrahash = {2539e4acde94eda78c7e5aa821bf1bd5}, journal = {Journal of Organometallic Chemistry}, keywords = {Raman Raman;charge Raman;chromium Raman;hybridization Raman;tungsten carbonyl carbonyltetracyanoethane charge chromium complex metal tetracyanoethane transfer transfer;cyanoethane tungsten}, number = {1-2}, pages = {189--195}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Resonance Raman study of (\textgreek{h}2-TCNE)M(CO)5 (M = Cr, W; TCNE = tetracyanoethene). Evidence for an olefin-complex $\rightarrow$ metallacyclopropane transition upon low-energy metal-to-ligand charge-transfer excitation}, volume = 409, year = 1991 }