PUMA publications for /user/b_schwederski/electrochem;tetrazinehttps://puma.ub.uni-stuttgart.de/user/b_schwederski/electrochem;tetrazinePUMA RSS feed for /user/b_schwederski/electrochem;tetrazine2024-03-28T21:18:42+01:00Metal-Induced Reductive Ring Opening of 1,2,4,5-Tetrazines: Three Resulting Coordination Alternatives, Including the New Non-Innocent 1,2-Diiminohydrazido(2-) Bridging Ligand Systemhttps://puma.ub.uni-stuttgart.de/bibtex/2e911cfa6a076cb23c9feb87a375f9702/b_schwederskib_schwederski2019-07-15T13:41:23+02:00acetylacetonato complex;ruthenium crystal diiminohydrazido dinuclear electrochem;tetrazine induced opening prepn ring 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/16f001ef897f74cb73ba45e5296398ebc/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/16f001ef897f74cb73ba45e5296398ebc/author/1"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Srikanta Patra" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/author/2"><span itemprop="name">S. Patra</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/author/3"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Shaikh M. Mobin" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/author/4"><span itemprop="name">S. Mobin</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Vedavati G. Puranik" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/author/5"><span itemprop="name">V. Puranik</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/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="Goutam Kumar. Lahiri" itemprop="url" href="/person/16f001ef897f74cb73ba45e5296398ebc/author/7"><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">45 </span></span>(<span itemprop="issueNumber">3</span>):
<span itemprop="pagination">1316--1325</span></em> </span>(<em><span>2006<meta content="2006" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry31316--1325Metal-Induced Reductive Ring Opening of 1,2,4,5-Tetrazines: Three Resulting Coordination Alternatives, Including the New Non-Innocent 1,2-Diiminohydrazido(2-) Bridging Ligand System452006acetylacetonato complex;ruthenium crystal diiminohydrazido dinuclear electrochem;tetrazine induced opening prepn ring ruthenium structure Reaction of 3,6-diaryl-1,2,4,5-tetrazines (aryl = R = Ph, 2-furyl or 2-thienyl) with 2 equiv of Ru(acac)2(CH3CN)2 results in reductive tetrazine ring opening to yield diruthenium complexes [(acac)2RuIII(dih-R2-)RuIII(acac)2] bridged by the new 1,2-diiminohydrazido(2-) (dih-R2- = HNC(R)NNC(R)NH2-) ligands. Rac/meso diastereoisomers could be detected and sepd. for the compds. with R = Ph and 2-thienyl, all species are diamagnetic and were characterized by 1H NMR spectroscopy. Crystal structure detn. of the meso isomers with R = Ph and 2-thienyl confirmed the 1,2-diiminohydrazido formulation through long N-N ($\approx$1.40 {\AA}) and short C:N(H) bonds ($\approx$1.31 {\AA}), implying two bridged ruthenium(III) centers at $\sim$4.765 {\AA} distance with strong antiferromagnetic coupling. The complexes undergo two reversible and well-sepd. 1-electron redn. and oxidn. processes, resp. EPR Spectroscopy of the paramagnetic intermediates with comproportionation consts. Kc {\textgreater} 1012 and UV-visible-NIR spectroelectrochem. were used to identify the accessible redox states as [(acac)2RuII(dih-R2-)RuII(acac)2]2-, [(acac)2RuII(dih-R.bul.-)RuII(acac)2]-, [(acac)2RuIII(dih-R2-)RuIII(acac)2], [(acac)2RuIII(dih-R.bul.-)RuIII(acac)2]+, and [(acac)2RuIII(dih-R)RuIII(acac)2]2+. While the UV-visible-NIR spectroscopic response of [(acac)2Ru(dih-R)Ru(acac)2]0/-/2- is very similar to that of [(bpy)2Ru(adc-R)Ru(bpy)2]4+/3+/2+, adc-R2- = 1,2-diacylhydrazido(2-), the EPR result indicating ligand-centered spin for [(acac)2RuII(dih-R.bul.-)RuII(acac)2]- despite deceptive NIR absorptions around 1400 nm reveals distinct differences in the electronic structures. [on SciFinder(R)]