PUMA publications for /user/b_schwederski/osmiumhttps://puma.ub.uni-stuttgart.de/user/b_schwederski/osmiumPUMA RSS feed for /user/b_schwederski/osmium2024-03-28T12:22:10+01:00Metal(IV) Complexes M(LN,O,S)2n (M = Ru, Os) of a Redox-Active o-Amidophenolate Ligand (LN,O,S)2- with Coordinating Thioether Appendixhttps://puma.ub.uni-stuttgart.de/bibtex/26e4cd4cfc8cd4b746b17ae4598d2c209/b_schwederskib_schwederski2019-07-15T13:41:23+02:00calcn complex complex;DFT complex;ESR complex;mononuclear crystal cyclic mononuclear osmium prepn ruthenium spectra structure;UV thiophenylamidophenolate tridentate voltammetry <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ralph Huebner" itemprop="url" href="/person/19e5e2b2f261b10914a488a74a92a0e27/author/0"><span itemprop="name">R. Huebner</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/19e5e2b2f261b10914a488a74a92a0e27/author/1"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/19e5e2b2f261b10914a488a74a92a0e27/author/2"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/19e5e2b2f261b10914a488a74a92a0e27/author/3"><span itemprop="name">S. Zalis</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/19e5e2b2f261b10914a488a74a92a0e27/author/4"><span itemprop="name">W. Kaim</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">European Journal of Inorganic Chemistry</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">2012 </span></span>(<span itemprop="issueNumber">22</span>):
<span itemprop="pagination">3569-3576, S3569/1-S3569/5</span></em> </span>(<em><span>2012<meta content="2012" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019European Journal of Inorganic Chemistry223569-3576, S3569/1-S3569/5Metal(IV) Complexes [M(LN,O,S)2]n (M = Ru, Os) of a Redox-Active o-Amidophenolate Ligand (LN,O,S)2- with Coordinating Thioether Appendix20122012calcn complex complex;DFT complex;ESR complex;mononuclear crystal cyclic mononuclear osmium prepn ruthenium spectra structure;UV thiophenylamidophenolate tridentate voltammetry Complexes [M(LN,O,S)2] [M = Ru, Os; (LN,O,S)2- = 4,6-di-tert-butyl(2-methylthiophenylamido)-o-phenolate] were obtained and structurally characterized as metal(IV) complexes with mer-configured tridentate ligands. Two reversible oxidns. and one (Os) or two (Ru) reversible redns. were studied by EPR and UV/visible/NIR spectroelectrochem. The first redn. leads to EPR-silent MIII species, whereas the oxidn. produces iminosemiquinone complexes with ligand-centered spin and small-metal participation at the singly occupied MO. Absorptions in the visible and near-IR region are assigned with the help of time-dependent (TD)-DFT calcns. [on SciFinder(R)]Spectroelectrochemical Characterization of the Two-Step Redox System (μ-pz)Os(CN)52n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube Systemhttps://puma.ub.uni-stuttgart.de/bibtex/261a3027331a4e00bf7609eb4df8ec796/b_schwederskib_schwederski2019-07-15T13:41:23+02:00charge cyano dinuclear dinuclear;electrochem dinuclear;osmium osmium oxidn prepn pyrazine spectra spectroelectrochem transfer <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Fridmann M. Hornung" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/0"><span itemprop="name">F. Hornung</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Frank Baumann" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/1"><span itemprop="name">F. Baumann</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/2"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jose A. Olabe" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/3"><span itemprop="name">J. Olabe</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Leonardo D. Slep" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/4"><span itemprop="name">L. Slep</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan. Fiedler" itemprop="url" href="/person/1057634afbb06e23404b862562371db5c/author/5"><span itemprop="name">J. Fiedler</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Inorganic Chemistry</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">37 </span></span>(<span itemprop="issueNumber">2</span>):
<span itemprop="pagination">311--316</span></em> </span>(<em><span>1998<meta content="1998" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry2311--316Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System371998charge cyano dinuclear dinuclear;electrochem dinuclear;osmium osmium oxidn prepn pyrazine spectra spectroelectrochem transfer The pyrazine-bridged diosmium(II) complex {(μ-C4H4N2)[Os(CN)5]2}6- was synthesized as the hexapotassium salt and was converted to the Bu4N+ salt compd. by ion exchange. Its stepwise oxidn. to the OsIII2OsII and OsIII2OsIII states was monitored spectroelectrochem. in MeCN/0.1 M Bu4NPF6 in the UV-visible-NIR and IR regions and by EPR. The OsII2 species exhibits long-wavelength solvatochromic MLCT bands at 14,800 and 18,480 cm-1. The pentaanionic mixed-valent ion has a comproportionation const. Kc of 105.8 and is distinguished by several electronic absorptions in the IR region. The bands at 1970, 2480, 4000, 5000, 7170, and 11,900 cm-1 are similar but appreciably lower in energy than those reported for the analogous complex {(μ-C4H4N2)[Os(NH3)5]2}5+. In addn. to CN vibrational stretching features shifted on electron transfer there is an addnl. sharp band only for the 5- ion at 1582 cm-1 which is attributed to a pyrazine ring vibration. The intensity of this band suggests an unsym. situation and thus valence localization on the vibrational time scale. The EPR signals at g$\bot$ = 2.0563 and g‖ = 1.761 point toward excited states lying close to the doublet ground state and to significant metal/cyanide interaction. Compared to the Creutz-Taube ion {(μ-C4H4N2)[Ru(NH3)5]2}5+ and its Os homolog, the 5- ion described here exhibits a lower degree of metal-metal coupling. [on SciFinder(R)]Characterization of the inorganic/organometallic osmium(IV) compound Cp*2OsIVCl2OsIVCl6 as formed by the reaction of OsCl3 with pentamethylcyclopentadiene in airhttps://puma.ub.uni-stuttgart.de/bibtex/2bb445aa7d0f0686c7d004be1091cda66/b_schwederskib_schwederski2019-07-15T13:41:23+02:00chloroosmate chloroosmate;pentamethylcyclopentadiene complexation crystal osmium pentamethylcyclopentadienyl prepn;mol structure trichloride <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Torsten Sixt" itemprop="url" href="/person/13df3ad72155d7f428293382695810b41/author/0"><span itemprop="name">T. Sixt</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/13df3ad72155d7f428293382695810b41/author/1"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wilhelm. Preetz" itemprop="url" href="/person/13df3ad72155d7f428293382695810b41/author/2"><span itemprop="name">W. Preetz</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">55 </span></span>(<span itemprop="issueNumber">3/4</span>):
<span itemprop="pagination">235--237</span></em> </span>(<em><span>2000<meta content="2000" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences3/4235--237Characterization of the inorganic/organometallic osmium(IV) compound [Cp*2OsIVCl]2[OsIVCl6] as formed by the reaction of OsCl3 with pentamethylcyclopentadiene in air552000chloroosmate chloroosmate;pentamethylcyclopentadiene complexation crystal osmium pentamethylcyclopentadienyl prepn;mol structure trichloride Reaction of OsCl3 with pentamethylcyclopentadiene in EtOH in air yields the ionic Os(IV) compd. [Cp*2OsCl]2[OsCl6] which was identified structurally and by vibrational spectroscopy. Under comparable conditions the RuCl3 homolog yields the Ru(III) compd. [Cp*RuCl2]2, illustrating the more facile oxidn. of the 5d element to the tetravalent state. [on SciFinder(R)]The Redox Series M(bpy)2(Q)n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1)https://puma.ub.uni-stuttgart.de/bibtex/25fc0d5ed98f13e18f2a58e906ea1c77c/b_schwederskib_schwederski2019-07-15T13:41:23+02:00EPR benzoquinonemonoimine osmium potential potential;ruthenium prepn redox spectroelectrochem <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Shengfa Ye" itemprop="url" href="/person/18bb616c087529a8c7a4a8523fed3f674/author/0"><span itemprop="name">S. Ye</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/18bb616c087529a8c7a4a8523fed3f674/author/1"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Carole Duboc" itemprop="url" href="/person/18bb616c087529a8c7a4a8523fed3f674/author/2"><span itemprop="name">C. Duboc</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/18bb616c087529a8c7a4a8523fed3f674/author/3"><span itemprop="name">J. Fiedler</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/18bb616c087529a8c7a4a8523fed3f674/author/4"><span itemprop="name">W. Kaim</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Inorganic Chemistry</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">44 </span></span>(<span itemprop="issueNumber">8</span>):
<span itemprop="pagination">2843--2847</span></em> </span>(<em><span>2005<meta content="2005" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry82843--2847The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1)442005EPR benzoquinonemonoimine osmium potential potential;ruthenium prepn redox spectroelectrochem [M(bpy)2(Q)](PF6) (bpy = 2,2'-bipyridyl; M = Ru, Os; Q = 3,5-di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine) were isolated and studied by X and W band EPR in a CH2Cl2 soln. at ambient temps. and at 4 K. For M = Ru, the 14N hyperfine splitting confirms the RuII/semiquinone formulation, although at a {\textgreater} 1 mT, the 99,101Ru satellite coupling is unusually high. W band EPR allowed the authors to det. the relatively small g anisotropy \textgreek{D}g = g1 - g3 = 0.0665 for the Ru complex. The Os analog exhibits a much higher difference \textgreek{D}g = 0.370, which is attributed not only to the larger spin-orbit coupling const. of Os vs. that of Ru but also to a higher extent of metal contribution to the singly occupied MO. The difference \textgreek{D}E between the oxidn. and redn. potentials of the radical complexes is larger for the Ru compd. (\textgreek{D}E = 0.87 V) than for the Os analog (\textgreek{D}E = 0.72), confirming the difference in metal/ligand interaction. The electrochem. generated states [M(bpy)2(Q)]n+, n = 0, 1, 2, and 3, were also characterized using UV-visible-near-IR spectroelectrochem. [on SciFinder(R)]Stepwise and chemically reversible reduction of (μ-bmtz)MCl(η6-cym)2PF62 (M = Ru, Os; bmtz = 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine) with up to six electronshttps://puma.ub.uni-stuttgart.de/bibtex/23da6415137a0b59d8ccdba43b2c4e02c/b_schwederskib_schwederski2019-07-15T13:41:23+02:00ESR cymene;ruthenium dinuclear electrochem osmium pyrimidyltetrazine redn redn;spectroelectrochem ruthenium <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Markus Glockle" itemprop="url" href="/person/1618f95dd74d3fbc580fd6ffadacfad23/author/0"><span itemprop="name">M. Glockle</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1618f95dd74d3fbc580fd6ffadacfad23/author/1"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan. Fiedler" itemprop="url" href="/person/1618f95dd74d3fbc580fd6ffadacfad23/author/2"><span itemprop="name">J. Fiedler</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Zeitschrift fuer Anorganische und Allgemeine Chemie</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">627 </span></span>(<span itemprop="issueNumber">7</span>):
<span itemprop="pagination">1441--1453</span></em> </span>(<em><span>2001<meta content="2001" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Zeitschrift fuer Anorganische und Allgemeine Chemie71441--1453Stepwise and chemically reversible reduction of {(μ-bmtz)[MCl(η6-cym)]2}[PF6]2 (M = Ru, Os; bmtz = 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine) with up to six electrons6272001ESR cymene;ruthenium dinuclear electrochem osmium pyrimidyltetrazine redn redn;spectroelectrochem ruthenium The title compds. were synthesized and characterized spectroscopically. Anal. of cyclic voltammetry in conjunction with spectroelectrochem. (UV/visible/NIR, ESR) allowed the authors to identify the products of sequential, chem. reversible redn. with up to six electrons. It is the first time that the mol. coupling of electron transfer steps (E) and bond breaking/bond forming chem. processes (C) was studied for a diruthenium system. In that case, the chem. reversible sequence E, EC, EEC, E and E was obsd. whereas the diosmium analog showed the unusual sequence E, EC, E, EEC and E. [on SciFinder(R)]