PUMA publications for /user/b_schwederski/spectrohttps://puma.ub.uni-stuttgart.de/user/b_schwederski/spectroPUMA RSS feed for /user/b_schwederski/spectro2024-03-28T10:00:55+01:00The FeIII/FeII vs. Fe22.5 Formulation in Mixed-Valent Species (NC)4Fe(BL)Fe(CN)43-, BL = 2,2'-Bipyrimidine and 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine. Distance and Size Do Not Always Matterhttps://puma.ub.uni-stuttgart.de/bibtex/28e2f987e1e023a3d30198c11e33af518/b_schwederskib_schwederski2019-07-15T13:41:23+02:00bipyrimidine complex complex;iron complex;redn complex;redox complex;spectroelectrochem cyano dinuclear electrochem iron potential prepn;oxidn spectro tetrazinebispyridine <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Markus Gloeckle" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/author/0"><span itemprop="name">M. Gloeckle</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/author/1"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Nestor E. Katz" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/author/2"><span itemprop="name">N. Katz</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Monica Garcia Posse" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/author/3"><span itemprop="name">M. Posse</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Edgardo H. Cutin" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/author/4"><span itemprop="name">E. Cutin</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan. Fiedler" itemprop="url" href="/person/1f7a3ea637057261ac5828dc4c1737e49/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">38 </span></span>(<span itemprop="issueNumber">14</span>):
<span itemprop="pagination">3270--3274</span></em> </span>(<em><span>1999<meta content="1999" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry143270--3274The FeIII/FeII vs. Fe22.5 Formulation in Mixed-Valent Species [(NC)4Fe(BL)Fe(CN)4]3-, BL = 2,2'-Bipyrimidine and 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine. Distance and Size Do Not Always Matter381999bipyrimidine complex complex;iron complex;redn complex;redox complex;spectroelectrochem cyano dinuclear electrochem iron potential prepn;oxidn spectro tetrazinebispyridine Two mol.-bridged bis(tetracyanoiron) complexes [(NC)4Fe(BL)Fe(CN)4]n-, BL = 2,2'-bipyrimidine (bpym) and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), were studied by EPR, UV/visible/near-IR and IR spectroelectrochem. (n = 2-5) in aprotic media. Following these results, the Fe22.5 formulation is the correct valence description for the metal centers in the bptz-bridged trianion (Kc = 1014.6 in MeCN), whereas the localized FeIII/FeII formulation is appropriate for the bpym-bridged system (Kc = 105.4 in MeCN and 106.4 in CH2Cl2). In contrast to common perception, the larger tetrazine-bridged system with the longer metal-metal distance exhibits much stronger metal-metal coupling than the bpym-bridged analog, a consequence of the very low lying \textgreek{p}* LUMO of tetrazines with high MO coeffs. at the coordinating N centers. [on SciFinder(R)]