%0 Journal Article %1 Hilgers.1996 %A Hilgers, Frank %A Bruns, Wolfgang %A Fiedler, Jan %A Kaim, Wolfgang. %D 1996 %J Journal of Organometallic Chemistry %K alkylpyrazinium alkylpyrazinium;spectra carbonyl electrochem electrochem;redox molybdenum phosphine tungsten %N 1-2 %P 273--280 %R 10.1016/0022-328X(95)05933-G %T UV-visible, IR and EPR spectroelectrochemical study of the EC redox transition (PR3)n(CO)3(R'-pz)M+·; M = Mo, W; R'-pz = N-alkylpyrazinium; R = isopropyl, cyclohexyl; n = 1 or 2 %V 511 %X The title complexes, isolated as trans,mer-configurated salts (PR3)2(CO)3(R'-pz)M(PF6), display a strong p interaction between the zerovalent metal center and the excellent p acceptor ligands R-pz+. The solvatochromism of the long-wavelength metal-to-ligand charge transfer (MLCT) absorption as analyzed in particular for (PCy3)2(CO)3(CH3(CH2)17-pz)W(PF6) correlates not with established MLCT parameters but with the donor nos. of the solvents. The seemingly reversible 1-electron oxidn. and redn. processes were studied by spectroelectrochem. techniques with regard to EPR, carbonyl vibrational and UV-visible/NIR spectroscopic features. Whereas oxidn. leads to labile M(I) species with 17 valence electrons, the redn. is centered at the R'-pz+ ligand and causes a rapid reversible dissocn. of one PR3 group from the metal (ECrev process). Both EPR and IR data suggest pentacoordination at the 16+d valence electron centers in the neutral species (PR3)(CO)3(R'-pz)M·. on SciFinder(R)

@article{Hilgers.1996, abstract = {The title complexes, isolated as trans,mer-configurated salts [(PR3)2(CO)3(R'-pz)M](PF6), display a strong \textgreek{p} interaction between the zerovalent metal center and the excellent \textgreek{p} acceptor ligands R-pz+. The solvatochromism of the long-wavelength metal-to-ligand charge transfer (MLCT) absorption as analyzed in particular for [(PCy3)2(CO)3(CH3(CH2)17-pz)W](PF6) correlates not with established MLCT parameters but with the donor nos. of the solvents. The seemingly reversible 1-electron oxidn. and redn. processes were studied by spectroelectrochem. techniques with regard to EPR, carbonyl vibrational and UV-visible/NIR spectroscopic features. Whereas oxidn. leads to labile M(I) species with 17 valence electrons, the redn. is centered at the R'-pz+ ligand and causes a rapid reversible dissocn. of one PR3 group from the metal (ECrev process). Both EPR and IR data suggest pentacoordination at the 16+\textgreek{d} valence electron centers in the neutral species [(PR3)(CO)3(R'-pz)M]·. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Hilgers, Frank and Bruns, Wolfgang and Fiedler, Jan and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c8d2c0692a28d44c9e29e910718be8b2/huebleriac}, doi = {10.1016/0022-328X(95)05933-G}, interhash = {5d975b93b6fa5371c979c799049fbe73}, intrahash = {c8d2c0692a28d44c9e29e910718be8b2}, journal = {Journal of Organometallic Chemistry}, keywords = {alkylpyrazinium alkylpyrazinium;spectra carbonyl electrochem electrochem;redox molybdenum phosphine tungsten}, number = {1-2}, pages = {273--280}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {UV-visible, IR and EPR spectroelectrochemical study of the EC redox transition [(PR3)n(CO)3(R'-pz)M]+·; M = Mo, W; R'-pz = N-alkylpyrazinium; R = isopropyl, cyclohexyl; n = 1 or 2}, volume = 511, year = 1996 }