PUMA publications for /user/b_schwederski/dirhodiumhttps://puma.ub.uni-stuttgart.de/user/b_schwederski/dirhodiumPUMA RSS feed for /user/b_schwederski/dirhodium2024-03-29T03:28:41+01:00Electronic coupling of two Cp*ClM+/Cp*M reaction centers via p conjugated bridging ligands: Similarities and differences between rhodium and iridium analogueshttps://puma.ub.uni-stuttgart.de/bibtex/2207a9db70fd4da839eefa50d88c2dc6b/b_schwederskib_schwederski2019-07-15T13:41:23+02:00bidentate binuclear bispyridinyltetrazine center;iridium complex coupling diiridium dirhodium electron intermediate iridium redn redox rhodium spectroelectrochem;mixed tetrazinebispyrinyl valent <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/108213d42a7315c8f999a4336b09d45e5/author/0"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sascha Berger" itemprop="url" href="/person/108213d42a7315c8f999a4336b09d45e5/author/1"><span itemprop="name">S. Berger</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stefan Greulich" itemprop="url" href="/person/108213d42a7315c8f999a4336b09d45e5/author/2"><span itemprop="name">S. Greulich</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ralf Reinhardt" itemprop="url" href="/person/108213d42a7315c8f999a4336b09d45e5/author/3"><span itemprop="name">R. Reinhardt</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan. Fiedler" itemprop="url" href="/person/108213d42a7315c8f999a4336b09d45e5/author/4"><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">Journal of Organometallic Chemistry</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">582 </span></span>(<span itemprop="issueNumber">2</span>):
<span itemprop="pagination">153--159</span></em> </span>(<em><span>1999<meta content="1999" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Journal of Organometallic Chemistry2153--159Electronic coupling of two [Cp*ClM]+/[Cp*M] reaction centers via \textgreek{p} conjugated bridging ligands: Similarities and differences between rhodium and iridium analogues5821999bidentate binuclear bispyridinyltetrazine center;iridium complex coupling diiridium dirhodium electron intermediate iridium redn redox rhodium spectroelectrochem;mixed tetrazinebispyrinyl valent Dinuclear [Cp*ClM(\textgreek{m}-L)MClCp*](PF6)2, M = Rh or Ir, L = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) or 2,5-bis(phenyliminoethyl)pyrazine (bpip), are reduced in several chem. reversible steps by up to six electrons to [Cp*M(\textgreek{m}-L)MCp*]n-. UV-visible/NIR spectroelectrochem. and EPR of the paramagnetic states were used to identify the various intermediates. The complexes clearly show a reversible, ligand-centered 1-electron redn. (E) preceding the 1st chloride-dissociative metal redn. step (EC). Metal-metal interaction via the bridging \textgreek{p} acceptor ligand L causes a splitting of 310-710 mV between the potentials for the two Cl--dissociative steps. The 2nd chloride release occurs in EC+E fashion for L = bpip but in a two-electron process for L = bptz. The MIIMI mixed-valent species [Cp*M(\textgreek{m}-L)MCp*]+ could be identified via long-wavelength bands from intervalence charge transfer (IVCT) transitions. All complexes contg. at least one chloride-free Cp*M group display intense long-wavelength absorption bands. The Ir complexes are distinguished by more neg. potentials of the [Cp*Ir]-contg. forms, by slower formation of the M2I,II mixed-valent intermediate, by larger g anisotropy of the paramagnetic forms, and by triplet absorption features in the UV-visible electronic spectra. [on SciFinder(R)]Ligand-mediated coupling of organometallic reaction centershttps://puma.ub.uni-stuttgart.de/bibtex/2a9819eacbbe1ed03484734e6c90ae706/b_schwederskib_schwederski2019-07-15T13:41:23+02:00bidentate bispyridinyltetrazine center center;diiminopyrazine center;electrochem center;tetrazinebispyridinyl conjugation;ligand coupled coupling diiminopyrazine dirhodium extended mediated organometallic reaction redox <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/1b579fefb0b8d9a216070441e5e2a3794/author/0"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ralf Reinhardt" itemprop="url" href="/person/1b579fefb0b8d9a216070441e5e2a3794/author/1"><span itemprop="name">R. Reinhardt</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan. Fiedler" itemprop="url" href="/person/1b579fefb0b8d9a216070441e5e2a3794/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">Angewandte Chemie, International Edition in English</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">36 </span></span>(<span itemprop="issueNumber">22</span>):
<span itemprop="pagination">2493--2495</span></em> </span>(<em><span>1997<meta content="1997" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Angewandte Chemie, International Edition in English222493--2495Ligand-mediated coupling of organometallic reaction centers361997bidentate bispyridinyltetrazine center center;diiminopyrazine center;electrochem center;tetrazinebispyridinyl conjugation;ligand coupled coupling diiminopyrazine dirhodium extended mediated organometallic reaction redox In a systematic attempt to extend the coupling of electron transfer sites to the coupling of redox reaction centers through conjugated bridging ligands, [(C5Me5)ClRh(\textgreek{m}-L)RhCl(C5Me5)](PF6)2 (I) was prepd. from reaction of diiminopyrazine II or bis(pyridinyl)tetrazine III (\textgreek{m}-L) and [(C5Me5)RhCl2]2/AgPF6/acetone. I (as mixts. of cis and trans isomers) were studied by EPR and UV/Vis spectroscopy techniques and cyclic voltammetry to reveal extended and fully reversible electrochem.; the electrochem. potentials of I were reported. A communication between organometallic reaction sites in the dinuclear rhodium complexes bridged by ligands II and III is discussed. [on SciFinder(R)]