PUMA publications for /user/b_schwederski/mononuclearhttps://puma.ub.uni-stuttgart.de/user/b_schwederski/mononuclearPUMA RSS feed for /user/b_schwederski/mononuclear2024-03-28T16:24:45+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)]Configurational selectivity in benzyldimethylarsine complexes of palladium(II) and platinum(II): Synthesis, spectroscopy and structureshttps://puma.ub.uni-stuttgart.de/bibtex/207a2f3ef6fa31097e3b66e2af5ebf7b0/b_schwederskib_schwederski2019-07-15T13:41:23+02:00NMR;cis acetato benzyldimethylarsine benzyldimethylarsine;crystal bridged chloro cis correlation dinuclear halo isomer mononuclear palladium platinum prepn pyrazolato structure trans trans;platinum <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Prasad P. Phadnis" itemprop="url" href="/person/184a828c84e707709202dc089040c0615/author/0"><span itemprop="name">P. Phadnis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Vimal K. Jain" itemprop="url" href="/person/184a828c84e707709202dc089040c0615/author/1"><span itemprop="name">V. Jain</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Axel Klein" itemprop="url" href="/person/184a828c84e707709202dc089040c0615/author/2"><span itemprop="name">A. Klein</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Michael Weber" itemprop="url" href="/person/184a828c84e707709202dc089040c0615/author/3"><span itemprop="name">M. Weber</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/184a828c84e707709202dc089040c0615/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">Inorganica Chimica Acta</span>, </em> </span>(<em><span>2003<meta content="2003" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganica Chimica Acta119--128Configurational selectivity in benzyldimethylarsine complexes of palladium(II) and platinum(II): Synthesis, spectroscopy and structures3462003NMR;cis acetato benzyldimethylarsine benzyldimethylarsine;crystal bridged chloro cis correlation dinuclear halo isomer mononuclear palladium platinum prepn pyrazolato structure trans trans;platinum Benzyldimethylarsine complexes of Pd(II) and Pt(II) [MX2(BzAsMe2)2] (X = Cl, Br, I), [M2Cl2(\textgreek{m}-Cl)2(BzAsMe2)2], [Pd2Cl2(\textgreek{m}-OAc)2(BzAsMe2)2], [Pd2Me2(\textgreek{m}-Cl)2(BzAsMe2)2] and [Pd2X2(\textgreek{m}-N-N)2(BzAsMe2)2] (M = Pd or Pt; N-N = pyrazolate (pz) or 3,5-dimethylpyrazolate (dmpz)) were prepd. All complexes were characterized by elemental anal., IR, UV-visible absorption and NMR (1H, 13C, 195Pt) spectroscopy. The mol. structures of [MX2(BzAsMe2)2] (M = Pt or Pd; X = Cl, Br or I) were established by NMR spectroscopy and single crystal x-ray diffraction anal. and reveal a clear dichotomy in soln. and in the solid between the compds. with X = Cl in a cis configuration and the trans configured bromide and iodide complexes. [on SciFinder(R)]Interaction of two equivalent electron transfer/atom transfer centers via 2,2'-bipyrimidine as bridging ligandhttps://puma.ub.uni-stuttgart.de/bibtex/2b70db6d9437eec6ec1774806e193a30b/b_schwederskib_schwederski2019-07-15T13:41:23+02:00atom bipyrimidine communication complex complex;electrochem complex;electron complex;electronic complex;mol complex;redox crystal cymene dinuclear electrochem mononuclear osmium structure transfer <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Frank Baumann" itemprop="url" href="/person/14ce20bd7007a940cd588ea64bee25b3f/author/0"><span itemprop="name">F. Baumann</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Andreas Stange" itemprop="url" href="/person/14ce20bd7007a940cd588ea64bee25b3f/author/1"><span itemprop="name">A. Stange</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/14ce20bd7007a940cd588ea64bee25b3f/author/2"><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 Communications</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">1 </span></span>(<span itemprop="issueNumber">8</span>):
<span itemprop="pagination">305--308</span></em> </span>(<em><span>1998<meta content="1998" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry Communications8305--308Interaction of two equivalent electron transfer/atom transfer centers via 2,2'-bipyrimidine as bridging ligand11998atom bipyrimidine communication complex complex;electrochem complex;electron complex;electronic complex;mol complex;redox crystal cymene dinuclear electrochem mononuclear osmium structure transfer The redox pair [(p-cym)OsCl]+/[(p-cym)Os], p-cym = \textgreek{h}6-p-cymene (1,4-C6H4MeiPr), involving a two electron process coupled with chloride dissocn., was studied in the mono- and dinuclear complex with the 2,2'-bipyrimidine (bpym) ligand. Whereas the mononuclear system exhibits the known ECE (electron transfer/chloride transfer/electron transfer) pattern on redn., the structurally characterized trans-{(μ-bpym)[(p-cym)OsCl]2}(PF6)2 shows several special features, including the decoupling of the 1st ECE process into an E and EC step (electron reservoir function of bpym) and a splitting of 420 mV for the redn. steps assocd. with the chloride transfer (electronic communication between EC reaction centers). [on SciFinder(R)]Noninnocence of Indigo: Dehydroindigo Anions as Bridging Electron-Donor Ligands in Diruthenium Complexeshttps://puma.ub.uni-stuttgart.de/bibtex/2b737a149bbdf14ad09feafbc488d5e97/b_schwederskib_schwederski2019-07-15T13:41:23+02:00complex;ruthenium crystal dehydroindigo dinuclear electrochem electronic mononuclear phenylazopyridine prepn ruthenium spectroelectrochem structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Prasenjit Mondal" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/0"><span itemprop="name">P. Mondal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Madhumita Chatterjee" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/1"><span itemprop="name">M. Chatterjee</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Alexa Paretzki" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/2"><span itemprop="name">A. Paretzki</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Katharina Beyer" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/3"><span itemprop="name">K. Beyer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/4"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/16d7dac3f148f458893ca6811c33edaef/author/5"><span itemprop="name">G. Lahiri</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">55 </span></span>(<span itemprop="issueNumber">6</span>):
<span itemprop="pagination">3105--3116</span></em> </span>(<em><span>2016<meta content="2016" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry63105--3116Noninnocence of Indigo: Dehydroindigo Anions as Bridging Electron-Donor Ligands in Diruthenium Complexes552016complex;ruthenium crystal dehydroindigo dinuclear electrochem electronic mononuclear phenylazopyridine prepn ruthenium spectroelectrochem structure Complexes of singly or doubly deprotonated indigo (H2Ind) with one or two [Ru(pap)2]2+ fragments (pap = 2-phenylazopyridine) were characterized exptl. [mol. structure, voltammetry, EPR, and UV-visible-near-IR spectroelectrochem.] and by time-dependent d. functional theory calcns. [Ru(pap)2(HInd-)]ClO4 ([1]ClO4) contains an intramol. NH...O hydrogen bond, whereas [{Ru(pap)2}2(\textgreek{m}-Ind2-)](ClO4)2 ([2](ClO4)2), isolated as the meso diastereoisomer with near-IR absorptions at 1162 and 991 nm, contains two metals bridged at 6.354 {\AA} distance by the bischelating indigo dianion. The spectroelectrochem. study of multiple reversible redn. and oxidn. processes of 2n (n = 4+, 3+, 2+, 1+, 0, 1-, 2-, 3-, 4-) reveals the stepwise addn. of electrons to the terminal \textgreek{p}-accepting pap ligands, whereas the oxidns. occur predominantly at the anionic indigo ligand, producing an EPR-identified indigo radical intermediate and revealing the suitability of deprotonated indigo as a \textgreek{s}- and \textgreek{p}-donating bischelating bridge. [on SciFinder(R)]Electronic Structure of the 16 Valence Electron Fragments M(CO)3(PR3)2 (M = Mo, W; R = iPr, Cy) in Their Complexes with H2, THF, and Three p-Conjugated Dinucleating Ligands: Electrochemistry and Spectroscopy of Different Oxidation Stateshttps://puma.ub.uni-stuttgart.de/bibtex/21516320099dda469aae674ac30f455cc/b_schwederskib_schwederski2019-07-15T13:41:23+02:00carbonyl dinuclear electrochem molybdenum mononuclear phosphine phosphine;molybdenum redox redox;tungsten tungsten <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Bruns" itemprop="url" href="/person/1ee16534744739108d0f9eb811f7b6c97/author/0"><span itemprop="name">W. Bruns</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1ee16534744739108d0f9eb811f7b6c97/author/1"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Eberhard Waldhoer" itemprop="url" href="/person/1ee16534744739108d0f9eb811f7b6c97/author/2"><span itemprop="name">E. Waldhoer</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Michael. Krejcik" itemprop="url" href="/person/1ee16534744739108d0f9eb811f7b6c97/author/3"><span itemprop="name">M. Krejcik</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">34 </span></span>(<span itemprop="issueNumber">3</span>):
<span itemprop="pagination">663--672</span></em> </span>(<em><span>1995<meta content="1995" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry3663--672Electronic Structure of the 16 Valence Electron Fragments M(CO)3(PR3)2 (M = Mo, W; R = iPr, Cy) in Their Complexes with H2, THF, and Three \textgreek{p}-Conjugated Dinucleating Ligands: Electrochemistry and Spectroscopy of Different Oxidation States341995carbonyl dinuclear electrochem molybdenum mononuclear phosphine phosphine;molybdenum redox redox;tungsten tungsten Mononuclear trans,mer-(PR3)2(CO)3M(L) (M = Mo, W; R = iPr, Cy; L = THF, \textgreek{h}2-H2) and dinuclear trans,mer-[(PR3)2(CO)3M]2(\textgreek{m}-L) with the sym. bridging ligands \textgreek{m}-L = pyrazine (pz), 4,4'-bipyridine (bp) and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine (4,4'-bptz) were studied by cyclic voltammetry and by IR, UV/visible/near-IR, and EPR spectroscopy. Oxidn. of the electron-rich and dissociatively labile (Mo {\textgreater} W) systems yields M(I) species, including stable (Kc {\textgreater} 106) mixed-valent d5/d6 cations {[(PiPr3)2(CO)3M]2(pz)}+. These mixed-valent complex ions exhibit complete delocalization on the vibrational time scale and show similar spectroscopic features as the structurally related Creutz-Taube ion {[(H3N)5Ru]2(μ-pz)}5+. Reversible two-electron oxidn. processes and thus no mixed-valent states were obsd. for the bp- and 4,4'-bptz-bridged ditungsten systems. Whereas the oxidn. of (PCy3)2(CO)3W(\textgreek{h}2-H2) is irreversible with the assumed loss of a proton, the solvates (PR3)2(CO)3M(THF) are reversibly oxidized and reduced, the latter process requiring rather neg. potentials. In nonpolar solvents the neutral dinuclear complexes display very intense and strikingly narrow charge transfer bands in the near-IR region, suggesting very little geometrical change between ground and MLCT excited states. One-electron redn. of the dinuclear complexes produces EPR-detectable radical anion complexes which show the loss of one PR3 ligand per metal center, i.e. the preference for a 16 + \textgreek{d} rather than an 18 + \textgreek{d} valence electron configuration. The tungsten-centered oxidn. of (PR3)2(CO)3W(L) is facilitated in the order L = mpz+, pz, H2, 4,4'-bptz, bp, and THF, illustrating quant. the well-balanced \textgreek{s}-donor and \textgreek{s}*- or \textgreek{p}*-acceptor characteristics of the H2 ligand. From the results of this study apparently the (PR3)2(CO)3M fragments are suited to bind H2 because of a very finely tuned combination of \textgreek{s}-acceptor and fairly strong but not excessive \textgreek{p}-donor characteristics, in addn. to the proper amt. of steric shielding. [on SciFinder(R)]A structurally characterised redox pair involving an indigo radical: Indigo based redox activity in complexes with one or two Ru(bpy)2 fragmentshttps://puma.ub.uni-stuttgart.de/bibtex/2c3de132b16a417d57d3dd16f5c2a9b32/b_schwederskib_schwederski2019-07-15T13:41:23+02:00DFT bipyridine complex crystal density dinuclear dinuclear;electrochem dinuclear;electron dinuclear;ruthenium electronic indigo mononuclear prepn redox ruthenium spin structure;spectroelectrochem transition <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Madhumita Chatterjee" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/0"><span itemprop="name">M. Chatterjee</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Prasenjit Mondal" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/1"><span itemprop="name">P. Mondal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Katharina Beyer" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/2"><span itemprop="name">K. Beyer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Alexa Paretzki" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/3"><span itemprop="name">A. Paretzki</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/4"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/1aadad110d6b4a72d9dd6b0fbd0c9bc12/author/5"><span itemprop="name">G. Lahiri</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> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">46 </span></span>(<span itemprop="issueNumber">15</span>):
<span itemprop="pagination">5091--5102</span></em> </span>(<em><span>2017<meta content="2017" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Dalton Transactions155091--5102A structurally characterised redox pair involving an indigo radical: Indigo based redox activity in complexes with one or two [Ru(bpy)2] fragments462017DFT bipyridine complex crystal density dinuclear dinuclear;electrochem dinuclear;electron dinuclear;ruthenium electronic indigo mononuclear prepn redox ruthenium spin structure;spectroelectrochem transition The reaction between indigo, H2Ind, and {Ru(bpy)2(EtOH)2}2+ in EtOH/NaOH produced [Ru(bpy)2(HInd)]ClO4 [1]ClO4, rac-{[Ru(bpy)2]2(μ-Ind)}(ClO4)2 [2](ClO4)2, and meso-{[Ru(bpy)2]2(μ-Ind)}(ClO4)3 [2](ClO4)3, which were structurally characterized, the latter as the first stable, isolable radical complex of indigo. The redox pair 22+/23+ showed little structural difference, as confirmed using DFT calcns. The redox series 1n and 2n were studied using voltammetry and spectroelectrochem. (EPR, UV-visible-NIR). Remarkably, the EPR results for 1, 12+, 2+ and 23+ revealed mostly ligand-based spin in Ru(II) complexes of the indigo-derived radical ligands HInd.bul.2-, HInd.bul., Ind.bul.3- and Ind.bul.-, in agreement with the DFT calcd. spin densities. The dominance of the frontier orbitals by the metal-stabilized indigo chromophore was also confirmed via the TD-DFT based assignment of near-IR absorptions as intra-indigo or ligand-to-ligand charge transfer transitions. [on SciFinder(R)]A DFT based assessment of coordination modes of the bis(1-methyl-2-imidazolyl)glyoxal ligand in mononuclear and dinuclear complexeshttps://puma.ub.uni-stuttgart.de/bibtex/28e2d23447faea484a543a9344446d20b/b_schwederskib_schwederski2019-07-15T13:41:23+02:00DFT complex dinuclear glyoxal imidazolyl ligand methyl mononuclear <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Orkan Sarper" itemprop="url" href="/person/12d1d37ee6162ffb706eb99eac1d725cd/author/0"><span itemprop="name">O. Sarper</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ece Bulak" itemprop="url" href="/person/12d1d37ee6162ffb706eb99eac1d725cd/author/1"><span itemprop="name">E. Bulak</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/12d1d37ee6162ffb706eb99eac1d725cd/author/2"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Tereza. Varnali" itemprop="url" href="/person/12d1d37ee6162ffb706eb99eac1d725cd/author/3"><span itemprop="name">T. Varnali</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 Molecular Structure: THEOCHEM</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">773 </span></span>(<span itemprop="issueNumber">1-3</span>):
<span itemprop="pagination">35--42</span></em> </span>(<em><span>2006<meta content="2006" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Journal of Molecular Structure: THEOCHEM1-335--42A DFT based assessment of coordination modes of the bis(1-methyl-2-imidazolyl)glyoxal ligand in mononuclear and dinuclear complexes7732006DFT complex dinuclear glyoxal imidazolyl ligand methyl mononuclear The ligand bis(1-methyl-2-imidazolyl)glyoxal (big) was studied by DFT with respect to energy min. conformations in the neutral, cation and anion radical states. Coordination alternatives involving chelate rings of different size were calcd. for the partly exptl. accessible mononuclear complexes of big with [AuCl2]+, [Rh(C5R5)Cl]+ and Re(CO)3Cl. Comparative DFT calcns. of various coordination modes for mononuclear, homodinuclear and heterodinuclear complexes of the potentially tetradentate big ligand reveal a preference for seven-membered chelate rings in the mononuclear species and for edge-sharing six-membered chelate rings with anti configuration of the metal-chloride bonds for the dinuclear systems, supporting the exptl. evidence obtained through spectroscopic and electrochem. studies of {(μ-big)[Re(CO)3Cl]2}. [on SciFinder(R)]Complexes of 1,3-bis(diphenylphosphino)propane (dppp) with dichloroplatinum(II) and bis(chlorogold(I)): Intramolecular versus intermolecular AuI-AuI association of (m-dppp)(AuCl)2 in catena and cyclo formshttps://puma.ub.uni-stuttgart.de/bibtex/2fa9a57a1d793755312336dd70a70f686/b_schwederskib_schwederski2019-07-15T13:41:23+02:00chloro complex complex;propanediphosphine crystal dinuclear gold mononuclear platinum prepn propanediphosphine structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/169571bc4c025c94cdd87d819e4b13a4f/author/0"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Akbey Dogan" itemprop="url" href="/person/169571bc4c025c94cdd87d819e4b13a4f/author/1"><span itemprop="name">A. Dogan</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Axel Klein" itemprop="url" href="/person/169571bc4c025c94cdd87d819e4b13a4f/author/2"><span itemprop="name">A. Klein</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav. Zalis" itemprop="url" href="/person/169571bc4c025c94cdd87d819e4b13a4f/author/3"><span itemprop="name">S. Zalis</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">631 </span></span>(<span itemprop="issueNumber">8</span>):
<span itemprop="pagination">1355--1358</span></em> </span>(<em><span>2005<meta content="2005" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Zeitschrift fuer Anorganische und Allgemeine Chemie81355--1358Complexes of 1,3-bis(diphenylphosphino)propane (dppp) with dichloroplatinum(II) and bis(chlorogold(I)): Intramolecular versus intermolecular AuI-AuI association of [(\textgreek{m}-dppp)(AuCl)2] in catena and cyclo forms6312005chloro complex complex;propanediphosphine crystal dinuclear gold mononuclear platinum prepn propanediphosphine structure [(\textgreek{m}-Dppp)(AuCl)2], previously reported to assoc. intermolecularly in a chain (catena) structure through Au1-Au1 interactions (3.316 {\AA}), was obtained from gold(III) precursors in a cyclo form with shortened intramol. AuI-AuI contacts at 3.237 {\AA} and a puckered AuPCCCPAu seven-membered ring. DFT calcns. using a large relativistic basis to account for the d10-d10 interaction reproduce the obsd. mol. structure in the crystal of this linkage isomer, including the conspicuous distortion at one of the gold atoms. The chelate complex [(dppp)PtCl2] was crystd. and structurally characterized as the dichloromethane solvate. [on SciFinder(R)]Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligandhttps://puma.ub.uni-stuttgart.de/bibtex/23f0a8309af359b6b9c7e5411a93708e3/b_schwederskib_schwederski2019-07-15T13:41:23+02:00acac bipyridine crystal dinuclear;ruthenium electron electronic mononuclear noninnocent phenylimineindigo prepn ruthenium spectroelectrochem structure transfer <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Prasenjit Mondal" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/0"><span itemprop="name">P. Mondal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sebastian Plebst" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/1"><span itemprop="name">S. Plebst</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ritwika Ray" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/2"><span itemprop="name">R. Ray</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Shaikh M. Mobin" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/3"><span itemprop="name">S. Mobin</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/4"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/16ce18fb32c0095709233a68fd2ed3738/author/5"><span itemprop="name">G. Lahiri</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">53 </span></span>(<span itemprop="issueNumber">17</span>):
<span itemprop="pagination">9348--9356</span></em> </span>(<em><span>2014<meta content="2014" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry179348--9356Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligand532014acac bipyridine crystal dinuclear;ruthenium electron electronic mononuclear noninnocent phenylimineindigo prepn ruthenium spectroelectrochem structure transfer In contrast to several reported coordination compds. of trans-Nindigo ligands [Nindigo = indigo-bis(N-phenylimine) = LH2] with one or two six-membered chelate rings involving one indole N and one extracyclic N for metal binding, the new diruthenium complex ion [(acac)2Ru(\textgreek{m},\textgreek{h}2:\textgreek{h}2-L)Ru(bpy)2]2+ = (2)2+ exhibits edge-sharing five- and seven-membered chelate rings in the 1st documented case of asym. bridging by a Nindigo ligand in the cis configuration [L2- = indigo-bis(N-phenylimine)dianion]. The dication in [2](ClO4)2 displays one Ru(\textgreek{a}-diimine)3 site and one Ru center with three neg. charged chelate ligands. [2](ClO4)2 was obtained from the [Ru(bpy)2]2+ contg. cis precursor [(LH)Ru(bpy)2]ClO4 = [1]ClO4, which exhibits cation intramol. H-bonding. Four accessible oxidn. states each were characterized for the 1n and 2n redox series with respect to metal- or ligand-centered electron transfer, based on x-ray structures, ESR, and UV-visible-near-IR spectroelectrochem. in conjunction with d. functional theory calcn. results. The structural asymmetry in the RuIII/RuII system 22+ is reflected by the electronic asymmetry (class I mixed-valence situation), leaving the noninnocent Nindigo bridge as the main redox-active site. [on SciFinder(R)]Non-innocent behaviour of ancillary and bridging ligands in homovalent and mixed-valent ruthenium complexes A2Ru(m-L)RuA2n, A = 2,4-pentanedionato or 2-phenylazopyridine, L2- = 2,5-bis(2-oxidophenyl)pyrazinehttps://puma.ub.uni-stuttgart.de/bibtex/2c3cc53f178b76e7a89ea71bf254bdc39/b_schwederskib_schwederski2019-07-15T13:41:23+02:00acetylacetonate complex crystal dinuclear electrochem hydroxyphenyl mononuclear pentanedionate phenylazopyridine prepn pyrazine pyrazine;ruthenium redox;spectroelectrochem ruthenium structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Somnath Maji" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/0"><span itemprop="name">S. Maji</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/1"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Shaikh M. Mobin" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/2"><span itemprop="name">S. Mobin</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/3"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/4"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/1e31c745f5cda892a66945c40f4e084e8/author/5"><span itemprop="name">G. Lahiri</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>2007<meta content="2007" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Dalton Transactions232411--2418Non-innocent behaviour of ancillary and bridging ligands in homovalent and mixed-valent ruthenium complexes [A2Ru(\textgreek{m}-L)RuA2]n, A = 2,4-pentanedionato or 2-phenylazopyridine, L2- = 2,5-bis(2-oxidophenyl)pyrazine2007acetylacetonate complex crystal dinuclear electrochem hydroxyphenyl mononuclear pentanedionate phenylazopyridine prepn pyrazine pyrazine;ruthenium redox;spectroelectrochem ruthenium structure Structurally characterized 2,5-bis(2-hydroxyphenyl)pyrazine (H2L) can be partially or fully deprotonated to form [(acac)2Ru(\textgreek{m}-L)Ru(acac)2], [1], acac- = acetylacetonato = 2,4-pentanedionato, [(pap)2Ru(\textgreek{m}-L)Ru(pap)2](ClO4)2, [2](ClO4)2, pap = 2-phenylazopyridine, or [(pap)2Ru(HL)](ClO4), [3](ClO4). Several reversible oxidn. and redn. processes were obsd. in each case and were analyzed with respect to oxidn. state alternatives through EPR and UV-visible-NIR spectroelectrochem. In relation to previously reported compds. with 2,2'-bipyridine as ancillary ligands the complex redox system [1]n is distinguished by a preference for metal-based electron transfer whereas the systems [2]n and [3]n favor an invariant RuII state. Accordingly, the paramagnetic forms of [1]n, n = -, 0, +, exhibit metal-centered spin whereas the odd-electron intermediates [2]+, [2]3+ and [3] show radical-type EPR spectra. A comparison with analogous complexes involving the 3,6-bis(2-oxidophenyl)-1,2,4,5-tetrazine reveals the diminished \textgreek{p} acceptor capability of the pyrazine-contg. bridge. [on SciFinder(R)]Stabilization of a Two-Coordinate Mononuclear Cobalt(0) Compoundhttps://puma.ub.uni-stuttgart.de/bibtex/2d6a5b0c4090e11bc06b01617fa4f5eb8/b_schwederskib_schwederski2019-07-15T13:41:23+02:00alkylamino carbene cobalt complex;stabilization crystal cyclic mol mononuclear structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Kartik Chandra Mondal" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/0"><span itemprop="name">K. Mondal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sudipta Roy" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/1"><span itemprop="name">S. Roy</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Susmita De" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/2"><span itemprop="name">S. De</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Pattiyil Parameswaran" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/3"><span itemprop="name">P. Parameswaran</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Birger Dittrich" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/4"><span itemprop="name">B. Dittrich</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Fabian Ehret" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/5"><span itemprop="name">F. Ehret</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/6"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Herbert W. Roesky" itemprop="url" href="/person/14412e1e11f071d7bb4451e6b3f63902a/author/7"><span itemprop="name">H. Roesky</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Chemistry - A European Journal</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">20 </span></span>(<span itemprop="issueNumber">37</span>):
<span itemprop="pagination">11646--11649</span></em> </span>(<em><span>2014<meta content="2014" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Chemistry - A European Journal3711646--11649Stabilization of a Two-Coordinate Mononuclear Cobalt(0) Compound202014alkylamino carbene cobalt complex;stabilization crystal cyclic mol mononuclear structure Compd. (Me2-cAAC:)2Co0 (2; Me2-cAAC: = cyclic (alkyl)amino carbene; :C(CH2)(CMe2)2N-2,6-iPr2C6H3) was synthesized by the redn. of the precursor (Me2-cAAC:)2CoICl (1) with KC8 in THF. The cyclic voltammogram of 1 exhibited one-electron redn., which suggests that synthesis of a bent 2-metallaallene (2) from 1 should be possible. Compd. 2 contains one cobalt atom in the formal oxidn. state zero, which is stabilized by two Me2-cAAC: ligands. Bond lengths from x-ray diffraction are 1.871(2) and 1.877(2) {\AA} with a C-Co-C bond angle of 170.12(8)°. The EPR spectrum of 2 exhibited a broad resonance attributed to the unique quasi-linear structure, which favors near degeneracy and gives rise to very rapid relaxation conditions. The cAAC-Co bond in 2 can be considered as a typical Dewar-Chatt-Duncanson type of bonding, which in turn retains 2.5 electron pairs on the Co atom as nonbonding electrons. [on SciFinder(R)]Coupling of organometallic reaction centers through the non-planar bridging ligand 2,3-bis(2-pyridyl)pyrazinehttps://puma.ub.uni-stuttgart.de/bibtex/2066fed5f0e9415fa90498794f7b1b9bf/b_schwederskib_schwederski2019-07-15T13:41:23+02:00binuclear bis complex complex;mol complex;redox complex;rhodium crystal half iridium mononuclear pentamethylcyclopentadienyl potential prepn pyridylpyrazine rhodium sandwich structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sascha Berger" itemprop="url" href="/person/11c6b6ae5b6175ca700b26ce93d9029cd/author/0"><span itemprop="name">S. Berger</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Thomas Scheiring" itemprop="url" href="/person/11c6b6ae5b6175ca700b26ce93d9029cd/author/1"><span itemprop="name">T. Scheiring</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/11c6b6ae5b6175ca700b26ce93d9029cd/author/2"><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/11c6b6ae5b6175ca700b26ce93d9029cd/author/3"><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">Zeitschrift fuer Anorganische und Allgemeine Chemie</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">630 </span></span>(<span itemprop="issueNumber">13-14</span>):
<span itemprop="pagination">2409--2417</span></em> </span>(<em><span>2004<meta content="2004" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Zeitschrift fuer Anorganische und Allgemeine Chemie13-142409--2417Coupling of organometallic reaction centers through the non-planar bridging ligand 2,3-bis(2-pyridyl)pyrazine6302004binuclear bis complex complex;mol complex;redox complex;rhodium crystal half iridium mononuclear pentamethylcyclopentadienyl potential prepn pyridylpyrazine rhodium sandwich structure Half-sandwich rhodium and iridium 2,3-bis(2-pyridyl)pyrazine (2,3-bppz) complexes were prepd. and characterized by crystal structure detns. and cyclic voltammetry. Reaction of [Cp*MCl2]2 with free 2,3-bppz afforded monomeric [Cp*MCl(2,3-bppz)][PF6], whereas the same reaction in the presence of AgPF6 gave dimeric [[Cp*MCl]2(\textgreek{m}-2,3-bppz)][PF6]2 (Cp* = \textgreek{h}5-C5Me5, M = Rh, Ir). Crystal structure of the monomeric iridium complex features essentially nonplanar 2,3-bppz ligand, coordinated by one of its pyrazine and pyridine nitrogens. The prepd. complexes were investigated by cyclic voltammetry and UV/VIS-spectroelectrochem. For both the mononuclear and, unusually, the dinuclear complexes only chloride-dissociative two-electron redn. processes were obsd. [on SciFinder(R)]Synthesis and mixed valence aspects of (L)ClRu2(m-tppz)n+ incorporating 2,2'-dipyridylamine (L) as ancillary and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) as bridging ligandhttps://puma.ub.uni-stuttgart.de/bibtex/277cf79c87db0ff4e4de08a72f9256ca7/b_schwederskib_schwederski2019-07-15T13:41:23+02:00complex complex;electrochem complex;luminescence complex;mixed complex;ruthenium comproportionation const dinuclear dipyridylamine mononuclear polypyridylpyrazine prepn ruthenium valence <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Nripen Chanda" itemprop="url" href="/person/10f25f049be3dc8819941b22919e4fbf8/author/0"><span itemprop="name">N. Chanda</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/10f25f049be3dc8819941b22919e4fbf8/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/10f25f049be3dc8819941b22919e4fbf8/author/2"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/10f25f049be3dc8819941b22919e4fbf8/author/3"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/10f25f049be3dc8819941b22919e4fbf8/author/4"><span itemprop="name">G. Lahiri</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>2003<meta content="2003" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Dalton Transactions183550--3555Synthesis and mixed valence aspects of [{(L)ClRu}2(\textgreek{m}-tppz)]n+ incorporating 2,2'-dipyridylamine (L) as ancillary and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) as bridging ligand2003complex complex;electrochem complex;luminescence complex;mixed complex;ruthenium comproportionation const dinuclear dipyridylamine mononuclear polypyridylpyrazine prepn ruthenium valence The tppz-bridged diruthenium complex [{(L)ClRuII}2(\textgreek{m}-tppz)](ClO4)2, [1](ClO4)2 {tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, L = 2,2'-dipyridylamine} and its mononuclear counterpart [(L)ClRuII(tppz)]ClO4, [2](ClO4) were synthesized. The 380 mV sepn. between successive RuII/RuIII couples in [1]2+ leads to a comproportionation const. (Kc) of 2.7 $\times$ 106. Consequently, the RuIIRuIII species [1]3+ exhibits a rather narrow intervalence charge transfer band at 1700 nm, suggesting a class III mixed-valence state, the electronic coupling const. (Vab) is calcd. at 2940 cm-1. [1]3+ Displays a rhombic EPR spectrum at 4 K (g1 = 3.390, g2 = 2.278, g3 = 1.697), characteristic of Ru(iii) in a distorted octahedral environment. Both complexes show two successive tppz-based redn. processes [(tppz)0/-1 and (tppz)-1/-2]. The 1-electron reduced species [1]+ is a tppz radical anion species with an intense low-energy band at 1105 nm and an axial EPR signal at 4 K (g1 = 2.008, g2 = g3 = 1.994). [1]2+ And [2]+ exhibit moderately strong emissions at 740 nm and 668 nm, resp., in EtOH-MeOH glass at 77 K. [on SciFinder(R)]Reactivity of copper(I) complexes with tripodal ligands towards O2: Structures of a precursor L3CuI(NCCH3)(BF4), L3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane and of its oxidation product L3CuII(m-OH)2CuIIL3(BF4)2 with strong antiferromagnetic spin-spin couplinghttps://puma.ub.uni-stuttgart.de/bibtex/2efde9d684da35614ffebc9aefc739ecf/b_schwederskib_schwederski2019-07-15T13:41:23+02:00acetonitrile antiferromagnetic complex complex;copper copper coupling dinuclear dinuclear;magnetic hydroxy methane mononuclear prepn property structure structure;crystal trimethylenepyrazolyl <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/0"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Christoph Titze" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/1"><span itemprop="name">C. Titze</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Thilo Schurr" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/2"><span itemprop="name">T. Schurr</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Monika Sieger" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/3"><span itemprop="name">M. Sieger</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Max Lawson" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/4"><span itemprop="name">M. Lawson</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jeanne Jordanov" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/5"><span itemprop="name">J. Jordanov</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Dario Rojas" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/6"><span itemprop="name">D. Rojas</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ana M. Garcia" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/7"><span itemprop="name">A. Garcia</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jorge. Manzur" itemprop="url" href="/person/1d396307cc93cf406e0e1d7951bb683be/author/8"><span itemprop="name">J. Manzur</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">631 </span></span>(<span itemprop="issueNumber">13-14</span>):
<span itemprop="pagination">2568--2574</span></em> </span>(<em><span>2005<meta content="2005" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Zeitschrift fuer Anorganische und Allgemeine Chemie13-142568--2574Reactivity of copper(I) complexes with tripodal ligands towards O2: Structures of a precursor [L3CuI(NCCH3)](BF4), L3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane and of its oxidation product [L3CuII(\textgreek{m}-OH)2CuIIL3](BF4)2 with strong antiferromagnetic spin-spin coupling6312005acetonitrile antiferromagnetic complex complex;copper copper coupling dinuclear dinuclear;magnetic hydroxy methane mononuclear prepn property structure structure;crystal trimethylenepyrazolyl The mol. structure of the highly oxygen-sensitive complex [L3CuI(NCCH3)](BF4) (1, L3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane) reveals approx. sym. coordination by the fac-tridentate (tripodal) ligand and a rather short CuI-N(acetonitrile) distance of 1.865(5) {\AA}. In CH2Cl2 at -78° the colorless compd. reacts with O2 to yield a labile purple intermediate (\textgreek{l}max 517 nm) - presumably a peroxodicopper(II) complex - which decomps. at -30°. No such intermediate was obsd. on reaction of the CuI complex of bis(2-pyridylmethyl)benzylamine with O2 at -80°. However, an EPR spectrum with g‖ = 2.17 and g$\bot$ = 2.03 without 63,65Cu hyperfine splitting was obsd. at low temps. Exposure of the precursor 1 to air under ambient conditions yields dinuclear [L3CuII(\textgreek{m}-OH)2CuIIL3](BF4)2 (2), which exhibits an EPR detectable dissocn. into monomers in CH2Cl2 soln. The structure of the hexakis(dichloromethane) solvate of 2 with Cu-Cu and Cu-O distances of 3.055 and 1.94 {\AA}, resp., is typical for dihydroxo-bridged dicopper compds. with square-pyramidal CuII configuration (\textgreek{t} = 0.03), adopting an anti arrangement. In agreement with the relatively wide Cu-O-Cu angles of 103.5°, an anal. of the temp. dependence of the magnetic susceptibility revealed a rather strong (J = -633 cm-1) antiparallel spin-spin coupling. The effect is ascribed to the steric bulk of the ligand L3. [on SciFinder(R)]Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexeshttps://puma.ub.uni-stuttgart.de/bibtex/24649810b900436c3ca29938481d0c1db/b_schwederskib_schwederski2019-07-15T13:41:23+02:00acac bipyridine complex complex;mol complex;prepn complex;redox crystal formazanato mononuclear noninnocent property ruthenium structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Abhishek Mandal" itemprop="url" href="/person/124a06ed89464cb9d9ee019461b955a61/author/0"><span itemprop="name">A. Mandal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Brigitte Schwederski" itemprop="url" href="/person/124a06ed89464cb9d9ee019461b955a61/author/1"><span itemprop="name">B. Schwederski</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/124a06ed89464cb9d9ee019461b955a61/author/2"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/124a06ed89464cb9d9ee019461b955a61/author/3"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam Kumar. Lahiri" itemprop="url" href="/person/124a06ed89464cb9d9ee019461b955a61/author/4"><span itemprop="name">G. Lahiri</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">54 </span></span>(<span itemprop="issueNumber">16</span>):
<span itemprop="pagination">8126--8135</span></em> </span>(<em><span>2015<meta content="2015" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry168126--8135Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexes542015acac bipyridine complex complex;mol complex;prepn complex;redox crystal formazanato mononuclear noninnocent property ruthenium structure Redox series of the complexes [Ru(L)(L')2]n, L = 1,5-diphenyl-3-(4-tolyl)-formazanate and L' = 2,4-pentanedionate (acac-), 2,2'-bipyridine (bpy), or 2-phenylazopyridine (pap), were studied by cyclic and differential pulse voltammetry and by TD-DFT-supported spectroelectrochem. (UV-visible-NIR, EPR). The prepd. complexes are [Ru(L-)(acac)2] (1), [Ru(L-)(bpy)2](ClO4) (2) , and [Ru(L-)(bpy)2](ClO4) (3). The precursors [RuIII(L-)(acac-)2], [RuII(L-)(bpy)2]ClO4, and [RuII(L-)(pap)2]ClO4 were identified in their indicated oxidn. states by x-ray crystal structure detn. The six-membered formazanato-ruthenium chelate rings have an envelope conformation with puckering of the metal. DFT calcns. indicate a pronounced sensitivity of the N-N bond lengths toward the ligand oxidn. state. Several electrochem. accessible charge states were analyzed, and the derived oxidn. nos. RuII, RuIII, or RuIV, L' or (L').bul.-, and L-, L.bul.2-, or the new formazanyl ligand L.bul. for the two-way noninnocent formazanate reflect the increasing acceptor effect of the ancillary ligands L' in the series acac- {\textless} bpy {\textless} pap. [on SciFinder(R)]1,4,7,10-Tetraazacyclododecane metal complexes as potent promoters of phosphodiester hydrolysis under physiological conditionshttps://puma.ub.uni-stuttgart.de/bibtex/2814a11c613dac1fa00a69191b2755407/b_schwederskib_schwederski2019-07-15T13:41:23+02:00binuclear bipyridinyl bridged catalyst catalyst;zinc hydrolysis kinetics mononuclear nitrophenyl phosphate pyridinyl tetraazacyclododecane triazine triazinyl zinc <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Michael Subat" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/0"><span itemprop="name">M. Subat</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Kristina Woinaroschy" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/1"><span itemprop="name">K. Woinaroschy</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Corinna Gerstl" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/2"><span itemprop="name">C. Gerstl</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/3"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/4"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Burkhard. Koenig" itemprop="url" href="/person/1c9b68881f09a0534cb86b01dff71630a/author/5"><span itemprop="name">B. Koenig</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">47 </span></span>(<span itemprop="issueNumber">11</span>):
<span itemprop="pagination">4661--4668</span></em> </span>(<em><span>2008<meta content="2008" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry114661--46681,4,7,10-Tetraazacyclododecane metal complexes as potent promoters of phosphodiester hydrolysis under physiological conditions472008binuclear bipyridinyl bridged catalyst catalyst;zinc hydrolysis kinetics mononuclear nitrophenyl phosphate pyridinyl tetraazacyclododecane triazine triazinyl zinc Previously reported mono- and dinuclear Zn(II), Cu(II), and Ni(II) complexes of 1,4,7,10-tetrazacyclododecane ([12]aneN4 or cyclen) with different heterocyclic spacers (triazine, pyridine, 2,2'-bipyridine), optionally contg. pendant azacrown ether moiety, exhibit catalytic activity in hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) in physiol. conditions (pH 7-9, 25°). All Zn(II) complexes promote the hydrolysis of BNPP under physiol. conditions, while those of Cu(II) and Ni(II) do not have a significant effect on the hydrolysis reaction. The hydrolysis rate consts. in buffered solns. (0.05 M Bis/Tris, TRIS, HEPES, or CHES, I = 0.1 M, NaCl) at 25° were detd. by the initial slope method at product conversion less than 5{\%}. Comparison of the second-order pH-independent rate consts. (kBNPP, M-1 s-1) for the zinc [12]aneN4 mononuclear complexes indicate that the pendant heterocyclic moiety, 4,6-dimethoxy-1,3,5-triazin-2-yl, 2-pyridinyl, 4-azacrown-6-methoxy-1,3,5-triazin-2-yl, improves the rate of hydrolysis up to six times over the parent Zn([12]aneN4) complex (kBNPP = 1.1 $\times$ 10-5 M-1 s-1). The reactive species is the Zn(II)-OH- complex, in which the Zn(II)-bound OH- acts as a nucleophile. For zinc dinuclear complexes, in which the [12]aneN4 moieties are bridged by 1,3,5-triazin-2,4-diyl or 2,2'-bipyridine-6,6'-diyl spacers, the rate of reaction is defined by the degree of cooperation between the metal centers, which is detd. by the spacer length. The complexes possessing shorter 1,3,5-triazin-2,4-diyl spacers are able to hydrolyze BNPP 1 to 2 orders of magnitudes faster than 2,2'-bipyridine-6,6'-diyl-bridged complex. The high BNPP hydrolytic activity may be related to \textgreek{p}-stacking and hydrophobic interactions between the arom. spacer moieties and the substrate. The tested complexes show hydrolytic activity at pH 7 and 8, which allows for the hydrolysis of activated phosphate esters under physiol. conditions. [on SciFinder(R)]1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled b-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexeshttps://puma.ub.uni-stuttgart.de/bibtex/26709b2814a058475e9ee49fb48f506b0/b_schwederskib_schwederski2019-07-15T13:41:23+02:00bipyridine complex complex;electrochem complex;ruthenium crystal diaminoanthracenedione dinuclear mononuclear phenyldiazenylpyridine prepn ruthenium spectroelectrochem structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Mohd. Asif Ansari" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/0"><span itemprop="name">M. Ansari</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Abhishek Mandal" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/1"><span itemprop="name">A. Mandal</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Alexa Paretzki" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/2"><span itemprop="name">A. Paretzki</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Katharina Beyer" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/3"><span itemprop="name">K. Beyer</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/4"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/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="Goutam Kumar. Lahiri" itemprop="url" href="/person/11a928eae2d766158e4047e82b4ea1ee9/author/6"><span itemprop="name">G. Lahiri</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">55 </span></span>(<span itemprop="issueNumber">11</span>):
<span itemprop="pagination">5655--5670</span></em> </span>(<em><span>2016<meta content="2016" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry115655--56701,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled \textgreek{b}-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes552016bipyridine complex complex;electrochem complex;ruthenium crystal diaminoanthracenedione dinuclear mononuclear phenyldiazenylpyridine prepn ruthenium spectroelectrochem structure The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asym. [(bpy)2Ru(\textgreek{m}-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosym. 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochem. of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidn. and redn. processes, which were analyzed by EPR of paramagnetic intermediates and by UV-visible-NIR spectro-electrochem. With support by time-dependent d. functional theory (DFT) calcns. the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 33+ vs. largely bridge-centered spin in 43+-a result of the presence of RuII-stabilizing pap coligands. In addn. to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asym. system 53+ with about equal contributions from a radical bridge formulation. In comparison to the analogs with the deprotonated 1,4-diaminoanthraquinone isomer the centrosym. H2L2- bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites. [on SciFinder(R)]