PUMA publications for /user/b_schwederski/dinuclear;magnetichttps://puma.ub.uni-stuttgart.de/user/b_schwederski/dinuclear;magneticPUMA RSS feed for /user/b_schwederski/dinuclear;magnetic2024-03-29T06:32:15+01:00Reactivity 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)]