PUMA publications for /tag/conjugation%20potentialhttps://puma.ub.uni-stuttgart.de/tag/conjugation%20potentialPUMA RSS feed for /tag/conjugation%20potential2024-03-29T09:10:20+01:00Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistryhttps://puma.ub.uni-stuttgart.de/bibtex/2ffc8ac9ac6e5c7681f8e0ed77243b8c9/huebleriachuebleriac2022-06-15T11:26:56+02:00ESR 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 <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Joerg Maurer" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/0"><span itemprop="name">J. Maurer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Michael Linseis" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/1"><span itemprop="name">M. Linseis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/2"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Brigitte Schwederski" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/3"><span itemprop="name">B. Schwederski</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Mark Niemeyer" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/4"><span itemprop="name">M. Niemeyer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/5"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/6"><span itemprop="name">S. Zalis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Chris Anson" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/7"><span itemprop="name">C. Anson</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Manfred Zabel" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/8"><span itemprop="name">M. Zabel</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Rainer F. Winter" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/9"><span itemprop="name">R. Winter</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Journal of the American Chemical Society</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">130 </span></span>(<span itemprop="issueNumber">1</span>):
<span itemprop="pagination">259--268</span></em> </span>(<em><span>2008<meta content="2008" itemprop="datePublished"/></span></em>)</span>Wed Jun 15 11:26:56 CEST 2022Journal of the American Chemical Society1259--268Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry1302008ESR 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 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)]Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistryhttps://puma.ub.uni-stuttgart.de/bibtex/2ffc8ac9ac6e5c7681f8e0ed77243b8c9/b_schwederskib_schwederski2019-07-15T13:41:23+02:00ESR 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 <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Joerg Maurer" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/0"><span itemprop="name">J. Maurer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Michael Linseis" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/1"><span itemprop="name">M. Linseis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/2"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Brigitte Schwederski" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/3"><span itemprop="name">B. Schwederski</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Mark Niemeyer" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/4"><span itemprop="name">M. Niemeyer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/5"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/6"><span itemprop="name">S. Zalis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Chris Anson" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/7"><span itemprop="name">C. Anson</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Manfred Zabel" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/8"><span itemprop="name">M. Zabel</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Rainer F. Winter" itemprop="url" href="/person/19784e4c65bc618f661506a3660a9a016/author/9"><span itemprop="name">R. Winter</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Journal of the American Chemical Society</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">130 </span></span>(<span itemprop="issueNumber">1</span>):
<span itemprop="pagination">259--268</span></em> </span>(<em><span>2008<meta content="2008" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Journal of the American Chemical Society1259--268Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry1302008ESR 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 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)]