%0 Journal Article %1 Maurer.2008 %A Maurer, Joerg %A Linseis, Michael %A Sarkar, Biprajit %A Schwederski, Brigitte %A Niemeyer, Mark %A Kaim, Wolfgang %A Zalis, Stanislav %A Anson, Chris %A Zabel, Manfred %A Winter, Rainer F. %D 2008 %J Journal of the American Chemical Society %K ESR carbonyl complex complex;crystal complex;mol complex;ruthenium conjugated conjugation effect electrooxidn;spectroelectrochem hexenyl oxidn phosphine pi potential prepn pyrenylethenyl pyridine ruthenium spectra structure styryl vinyl vinylruthenium %N 1 %P 259--268 %R 10.1021/ja075547t %T Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry %V 130 %X A series of vinylruthenium bis-phosphine five- and six-coordinated complexes with non-conjugated 1-hexenyl, conjugated styryl and pyrenylethenyl ligands were prepd.; the effects of conjugation of the arom. system with vinyl p-bond on oxidn. potential, stability of the oxidated species, ESR spectra and IR CO-stretching bands were systematically explored by IR-spectroelectrochem. and DFT calcns. Hydrometalation of 1-hexyne, phenylacetylene and 1-ethynylpyrene affords the corresponding five-coordinated ruthenium complexes [(PR3)2Cl(CO)RuCH:CHR1] (1a-3a; R = Ph, R1 = Bu, Ph, 1-pyrenyl; 1c-3c; R = iPr, same R1) and their octahedral pyridine adducts [(PPh3)2Cl(CO)(4-EtO2CC5H4N-kN)RuCH:CHR1] (1b-3b; same R1). Crystal structures of 1b, 1c, 3c and 3a·PPh3 and enynyl complex [Ru(CO)Cl(PPh3)2(h1:h2-nBuHC:CHC$\equiv$CnBu)], the result of coupling of the hexenyl ligand of complex 1a with another mol. of 1-hexyne, are reported. All vinyl complexes undergo a one-electron oxidn. at fairly low potentials and a second oxidn. at more pos. potentials. Anodic half-wave or peak potentials show a progressive shift to lower values as p-conjugation within the vinyl ligand increases. Carbonyl band shifts of the metal-bonded CO ligand upon monooxidn. are significantly smaller than is expected of a metal-centered oxidn. process and are further diminished as the vinyl CH:CH entity is incorporated into a more extended p-system. ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the av. g-value from that of the free electron. The vinyl ligands thus strongly contribute to or even dominate the anodic oxidn. processes. This renders them a class of truly \dqnon-innocent\dq ligands in organometallic ruthenium chem. Exptl. findings are fully supported by quantum chem. calcns. The contribution of the vinyl ligand to the HOMO increases from 46\% (Ru-vinyl delocalized) to 84\% (vinyl dominated) as R changes from Bu to 1-pyrenyl. [on SciFinder(R)]

@article{Maurer.2008, abstract = {A series of vinylruthenium bis-phosphine five- and six-coordinated complexes with non-conjugated 1-hexenyl, conjugated styryl and pyrenylethenyl ligands were prepd.; the effects of conjugation of the arom. system with vinyl \textgreek{p}-bond on oxidn. potential, stability of the oxidated species, ESR spectra and IR CO-stretching bands were systematically explored by IR-spectroelectrochem. and DFT calcns. Hydrometalation of 1-hexyne, phenylacetylene and 1-ethynylpyrene affords the corresponding five-coordinated ruthenium complexes [(PR3)2Cl(CO)RuCH:CHR1] (1a-3a; R = Ph, R1 = Bu, Ph, 1-pyrenyl; 1c-3c; R = iPr, same R1) and their octahedral pyridine adducts [(PPh3)2Cl(CO)(4-EtO2CC5H4N-\textgreek{k}N)RuCH:CHR1] (1b-3b; same R1). Crystal structures of 1b, 1c, 3c and 3a·PPh3 and enynyl complex [Ru(CO)Cl(PPh3)2(\textgreek{h}1:\textgreek{h}2-nBuHC:CHC$\equiv$CnBu)], the result of coupling of the hexenyl ligand of complex 1a with another mol. of 1-hexyne, are reported. All vinyl complexes undergo a one-electron oxidn. at fairly low potentials and a second oxidn. at more pos. potentials. Anodic half-wave or peak potentials show a progressive shift to lower values as \textgreek{p}-conjugation within the vinyl ligand increases. Carbonyl band shifts of the metal-bonded CO ligand upon monooxidn. are significantly smaller than is expected of a metal-centered oxidn. process and are further diminished as the vinyl CH:CH entity is incorporated into a more extended \textgreek{p}-system. ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the av. g-value from that of the free electron. The vinyl ligands thus strongly contribute to or even dominate the anodic oxidn. processes. This renders them a class of truly {\dq}non-innocent{\dq} ligands in organometallic ruthenium chem. Exptl. findings are fully supported by quantum chem. calcns. The contribution of the vinyl ligand to the HOMO increases from 46{\%} (Ru-vinyl delocalized) to 84{\%} (vinyl dominated) as R changes from Bu to 1-pyrenyl. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Maurer, Joerg and Linseis, Michael and Sarkar, Biprajit and Schwederski, Brigitte and Niemeyer, Mark and Kaim, Wolfgang and Zalis, Stanislav and Anson, Chris and Zabel, Manfred and Winter, Rainer F.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2ffc8ac9ac6e5c7681f8e0ed77243b8c9/huebleriac}, doi = {10.1021/ja075547t}, interhash = {9784e4c65bc618f661506a3660a9a016}, intrahash = {ffc8ac9ac6e5c7681f8e0ed77243b8c9}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {ESR carbonyl complex complex;crystal complex;mol complex;ruthenium conjugated conjugation effect electrooxidn;spectroelectrochem hexenyl oxidn phosphine pi potential prepn pyrenylethenyl pyridine ruthenium spectra structure styryl vinyl vinylruthenium}, number = 1, pages = {259--268}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry}, volume = 130, year = 2008 }