PUMA publications for /user/b_schwederski/osmium%20complex;osmium%20complex%20crystal%20complex;electronichttps://puma.ub.uni-stuttgart.de/user/b_schwederski/osmium%20complex;osmium%20complex%20crystal%20complex;electronicPUMA RSS feed for /user/b_schwederski/osmium%20complex;osmium%20complex%20crystal%20complex;electronic2024-03-29T14:06:51+01:00Effect of metal exchange (Os vs. Ru) and co-ligand variation (Cl- vs. acac-) on the oxidation state distribution in complexes of an o-phenylenediamido(2-)/o-quinonediimine redox systemhttps://puma.ub.uni-stuttgart.de/bibtex/2f0fe383261dd5a8922e54d89c729c7ca/b_schwederskib_schwederski2019-07-15T13:41:23+02:00complex complex;ESR complex;electronic complex;electrooxidn complex;electroredn complex;geometry complex;osmium complex;valence crystal optimized osmium prepn prepn;UV quinonediimine ruthenium structure structure;ruthenium visible <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sudipta Chatterjee" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/0"><span itemprop="name">S. Chatterjee</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Priti Singh" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/1"><span itemprop="name">P. Singh</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/2"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Radka Bakova" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/3"><span itemprop="name">R. Bakova</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/4"><span itemprop="name">S. Zalis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/5"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sreebrata. Goswami" itemprop="url" href="/person/100c0575ac5e250732a4d83f47899e198/author/6"><span itemprop="name">S. Goswami</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Dalton Transactions</span>, </em> </span>(<em><span>2009<meta content="2009" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Dalton Transactions377778--7785Effect of metal exchange (Os vs. Ru) and co-ligand variation (Cl- vs. acac-) on the oxidation state distribution in complexes of an o-phenylenediamido(2-)/o-quinonediimine redox system2009complex complex;ESR complex;electronic complex;electrooxidn complex;electroredn complex;geometry complex;osmium complex;valence crystal optimized osmium prepn prepn;UV quinonediimine ruthenium structure structure;ruthenium visible The compds. OsCl2L2 (1), RuCl2L2 (2) and Ru(acac)2L (3), L° = N-phenyl-o-quinonediimine and acac- = 2,4-pentanedionato, were synthesized and electrochem., spectroscopically and structurally characterized with the support of detailed DFT calcns. For the new Os compd. 1, the av. values for C:NH (1.331 {\AA}), C:NPh (1.345 {\AA}) and C:C (meta) bond lengths at 1.360 {\AA} agree more with an o-semiquinonediimine than with an o-quinonediimine formulation for the coordinated ligand, whereas the latter assignment is more appropriate to describe the Ru analog 2 (av. bond lengths of 1.308, 1.324, and 1.348 {\AA}, resp.). In turn, the corresponding av. bond lengths in 3 (1.333, 1.352, and 1.350 {\AA}, resp.) are suggestive of an o-semiquinonediimine ligand. DFT calcns. confirm the structural data and describe the electronic structures related to the oxidn. state assignments. The stabilization of trivalent Ru by electron donating acac- in 3 = RuIII(acac)2(L·-) and the preference of Os for higher oxidn. states (here: OsIVCl2(L·-)2 in 1) as compared to Ru analogs (here: RuIICl2(L°)2 in 2) in otherwise similar setting is responsible for these results. Oxidn. of the diamagnetic complexes proceeds to partly EPR and UV-visible spectroelectrochem. detectable cations with metal-centered spin, suggesting the following formulations: [OsIIICl2(L°)2]+ for 1+, [RuIIICl2(L°)2]+ for labile 2+, and [RuIII(acac)2(L°)]+ for 3+. In the case of 3, reversible metal-centered redn. results in ligand-based spin as compatible with a [RuII(acac)2(L·-)]- situation for 3-. [on SciFinder(R)]