PUMA publications for /user/b_schwederski/Group%20bipyrimidine%20carbonyl;grouphttps://puma.ub.uni-stuttgart.de/user/b_schwederski/Group%20bipyrimidine%20carbonyl;groupPUMA RSS feed for /user/b_schwederski/Group%20bipyrimidine%20carbonyl;group2024-03-29T06:14:43+01:00Four bridging bis chelate ligands with very low lying p* orbitals. MO perturbation calculations, electrochemistry, and spectroscopy of mononuclear and binuclear group 6 metal tetracarbonyl complexeshttps://puma.ub.uni-stuttgart.de/bibtex/232ee25b910134ec22e13a1b299291934/b_schwederskib_schwederski2019-07-15T13:41:23+02:00Group MO VIB azobipyridine bipyrimidine bischelant carbonyl;Group carbonyl;MO carbonyl;electronic carbonyl;energy electrochem electrochem;bipyrimidine electrochem;electrochem electrochem;pyridyltetrazine level pyridylpyrazine pyridyltetrazine;pyridylpyrazine transition <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/16939cad18951d07991ceb8002a8240c6/author/0"><span itemprop="name">W. Kaim</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stephan. Kohlmann" itemprop="url" href="/person/16939cad18951d07991ceb8002a8240c6/author/1"><span itemprop="name">S. Kohlmann</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">26 </span></span>(<span itemprop="issueNumber">1</span>):
<span itemprop="pagination">68--77</span></em> </span>(<em><span>1987<meta content="1987" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry168--77Four bridging bis chelate ligands with very low lying \textgreek{p}* orbitals. MO perturbation calculations, electrochemistry, and spectroscopy of mononuclear and binuclear group 6 metal tetracarbonyl complexes261987Group MO VIB azobipyridine bipyrimidine bischelant carbonyl;Group carbonyl;MO carbonyl;electronic carbonyl;energy electrochem electrochem;bipyrimidine electrochem;electrochem electrochem;pyridyltetrazine level pyridylpyrazine pyridyltetrazine;pyridylpyrazine transition Coordination characteristics of the 4 bridging, \textgreek{p}-delocalized bis chelate ligands 2,2'-bipyrimidine (bpym), 2,5-bis(2-pyridyl)pyrazine (bppz), 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), and azo-2,2'-bipyridine (abpy) were evaluated with use of \textgreek{p} MO perturbation calcns. and were studied exptl. by example of mononuclear and binuclear complexes with the fragments M(CO)4 (M = Cr, Mo, W). The substantial stabilization of the \textgreek{p}* (LUMO) levels in the order bpym, bppz, bptz, abpy strongly facilitates redn. of the complexes and causes shifts of the intense metal-to-ligand charge-transfer (LMCT) absorption bands out into the near-IR region. Despite a notable activation barrier for the formation of binuclear abpy complexes with 6-coordinate metals, (abpy)[Mo(CO)4]2 was prepd. and it exhibits most remarkable spectral properties such as an intense yet rather narrow and solvent-insensitive MLCT absorption band at 11,000 cm-1, another detectable absorption max. {\textgreater}30,000 cm-1, a redn. potential close to that of the ref. electrode, SCE, and closely spaced yet well-resolved CO stretching frequencies in the IR spectrum. All these spectral results can be correlated to \textgreek{p} MO calcn. data, which strongly suggest the use of bptz and abpy for studies concerned with ligand-mediated electronic interactions between metal centers. A particular asset of binuclear abpy complexes is the unusually short metal-metal distance caused by their coordination-induced S-frame conformation. [on SciFinder(R)]