PUMA publications for /tag/transfer;moessbauerhttps://puma.ub.uni-stuttgart.de/tag/transfer;moessbauerPUMA RSS feed for /tag/transfer;moessbauer2024-03-28T20:37:26+01:00Tetranuclear Complexes of Fe(CO)2(C5H5)+ with TCNX Ligands (TCNX = TCNE, TCNQ, TCNB): Intramolecular Electron Transfer Alternatives in Compounds (m4-TCNX)MLn4https://puma.ub.uni-stuttgart.de/bibtex/2c2d9f8d10c4e91bd2ae47cd61dba3dff/huebleriachuebleriac2022-06-15T11:26:56+02:00DFT EPR cyclopentadienyl dicarbonyl electrochem electron geometry iron redox structure tetracyanoethene tetracyanoquinodimethane transfer transfer;Moessbauer transfer;electronic transfer;optimized <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Amarendra N. Maity" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/0"><span itemprop="name">A. Maity</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Brigitte Schwederski" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/1"><span itemprop="name">B. Schwederski</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/2"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/3"><span itemprop="name">S. Zalis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/4"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sanjib Kar" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/5"><span itemprop="name">S. Kar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam K. Lahiri" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/6"><span itemprop="name">G. Lahiri</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Carole Duboc" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/7"><span itemprop="name">C. Duboc</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Matthias Grunert" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/8"><span itemprop="name">M. Grunert</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Philipp Guetlich" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/9"><span itemprop="name">P. Guetlich</span></a></span></span> and 1 other author(s). </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">46 </span></span>(<span itemprop="issueNumber">18</span>):
<span itemprop="pagination">7312--7320</span></em> </span>(<em><span>2007<meta content="2007" itemprop="datePublished"/></span></em>)</span>Wed Jun 15 11:26:56 CEST 2022Inorganic Chemistry187312--7320Tetranuclear Complexes of [Fe(CO)2(C5H5)]+ with TCNX Ligands (TCNX = TCNE, TCNQ, TCNB): Intramolecular Electron Transfer Alternatives in Compounds (\textgreek{m}4-TCNX)[MLn]4462007DFT EPR cyclopentadienyl dicarbonyl electrochem electron geometry iron redox structure tetracyanoethene tetracyanoquinodimethane transfer transfer;Moessbauer transfer;electronic transfer;optimized {(μ4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4 were prepd. as light-sensitive materials from [Fe(CO)2(C5H5)(THF)](BF4) and the corresponding TCNX ligands (TCNE = tetracyanoethene, TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, TCNB = 1,2,4,5-tetracyanobenzene). Whereas the TCNE and TCNQ complexes are extremely easily reduced species with redn. potentials {\textgreater}+0.3 V vs. ferrocenium/ferrocene, the tetranuclear complex of TCNB exhibits a significantly more neg. redn. potential at $\sim$-1.0 V. Even for the complexes with strongly \textgreek{p}-accepting TCNE and TCNQ, the very pos. redn. potentials, the unusually high nitrile stretching frequencies {\textgreater}2235 cm-1, and the high-energy charge-transfer transitions indicate negligible metal-to-ligand electron transfer in the ground state, corresponding to a largely unperturbed (TCNX°)(FeII)4 formulation of oxidn. states as caused by orthogonality between the metal-centered HOMO and the \textgreek{p}* LUMO of TCNX. Mossbauer spectroscopy confirms the low-spin Fe(II) state, and DFT calcns. suggest coplanar TCNE and TCNQ bridging ligands in the complex tetracations. One-electron redn. to the 3+ forms of the TCNE and TCNQ complexes produces EPR spectra which confirm the predominant ligand character of the then singly occupied MO through isotropic g values slightly {\textless}2, in addn. to a negligible g anisotropy of frozen solns. at frequencies up to 285 GHz and also through an unusually well-resolved soln. X band EPR spectrum of {(μ4-TCNE)[Fe(CO)2(C5H5)]4}3+ which shows four equiv. [Fe(CO)2(C5H5)]+ moieties through 57Fe and 13C(CO) hyperfine coupling in nonenriched material. DFT calcns. reproduce the exptl. EPR data. A survey of discrete TCNE and TCNQ complexes [(\textgreek{m}4-TCNX)(MLn)4] exhibits a dichotomy between the systems {(μ4-TCNX)[Fe(CO)2(C5H5)]4}4+ and {(μ4-TCNQ)[Re(CO)3(bpy)]4}4+ with their negligible metal-to-ligand electron transfer and several other compds. of TCNE or TCNQ with Mn, Ru, Os, or Cu complex fragments which display evidence for a strong such interaction, i.e., an appreciable value \textgreek{d} in the formulation {(μ4-TCNXδ-)[Mx+δ/4Ln]4}. Irreversibility of the 1st redn. of {(μ4-TCNB)[Fe(CO)2(C5H5)]4}(BF4)4 precluded spectroelectrochem. studies; however, the high-energy CN stretching frequencies and charge transfer absorptions of that TCNB analog also confirm the exceptional position of {(μ4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4. [on SciFinder(R)]Tetranuclear Complexes of Fe(CO)2(C5H5)+ with TCNX Ligands (TCNX = TCNE, TCNQ, TCNB): Intramolecular Electron Transfer Alternatives in Compounds (m4-TCNX)MLn4https://puma.ub.uni-stuttgart.de/bibtex/2c2d9f8d10c4e91bd2ae47cd61dba3dff/b_schwederskib_schwederski2019-07-15T13:41:23+02:00DFT EPR cyclopentadienyl dicarbonyl electrochem electron geometry iron redox structure tetracyanoethene tetracyanoquinodimethane transfer transfer;Moessbauer transfer;electronic transfer;optimized <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Amarendra N. Maity" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/0"><span itemprop="name">A. Maity</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Brigitte Schwederski" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/1"><span itemprop="name">B. Schwederski</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Biprajit Sarkar" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/2"><span itemprop="name">B. Sarkar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Stanislav Zalis" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/3"><span itemprop="name">S. Zalis</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jan Fiedler" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/4"><span itemprop="name">J. Fiedler</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Sanjib Kar" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/5"><span itemprop="name">S. Kar</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Goutam K. Lahiri" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/6"><span itemprop="name">G. Lahiri</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Carole Duboc" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/7"><span itemprop="name">C. Duboc</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Matthias Grunert" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/8"><span itemprop="name">M. Grunert</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Philipp Guetlich" itemprop="url" href="/person/10d6d985f3a7d15cf424c24b7e9f26385/author/9"><span itemprop="name">P. Guetlich</span></a></span></span> and 1 other author(s). </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">46 </span></span>(<span itemprop="issueNumber">18</span>):
<span itemprop="pagination">7312--7320</span></em> </span>(<em><span>2007<meta content="2007" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Inorganic Chemistry187312--7320Tetranuclear Complexes of [Fe(CO)2(C5H5)]+ with TCNX Ligands (TCNX = TCNE, TCNQ, TCNB): Intramolecular Electron Transfer Alternatives in Compounds (\textgreek{m}4-TCNX)[MLn]4462007DFT EPR cyclopentadienyl dicarbonyl electrochem electron geometry iron redox structure tetracyanoethene tetracyanoquinodimethane transfer transfer;Moessbauer transfer;electronic transfer;optimized {(μ4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4 were prepd. as light-sensitive materials from [Fe(CO)2(C5H5)(THF)](BF4) and the corresponding TCNX ligands (TCNE = tetracyanoethene, TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, TCNB = 1,2,4,5-tetracyanobenzene). Whereas the TCNE and TCNQ complexes are extremely easily reduced species with redn. potentials {\textgreater}+0.3 V vs. ferrocenium/ferrocene, the tetranuclear complex of TCNB exhibits a significantly more neg. redn. potential at $\sim$-1.0 V. Even for the complexes with strongly \textgreek{p}-accepting TCNE and TCNQ, the very pos. redn. potentials, the unusually high nitrile stretching frequencies {\textgreater}2235 cm-1, and the high-energy charge-transfer transitions indicate negligible metal-to-ligand electron transfer in the ground state, corresponding to a largely unperturbed (TCNX°)(FeII)4 formulation of oxidn. states as caused by orthogonality between the metal-centered HOMO and the \textgreek{p}* LUMO of TCNX. Mossbauer spectroscopy confirms the low-spin Fe(II) state, and DFT calcns. suggest coplanar TCNE and TCNQ bridging ligands in the complex tetracations. One-electron redn. to the 3+ forms of the TCNE and TCNQ complexes produces EPR spectra which confirm the predominant ligand character of the then singly occupied MO through isotropic g values slightly {\textless}2, in addn. to a negligible g anisotropy of frozen solns. at frequencies up to 285 GHz and also through an unusually well-resolved soln. X band EPR spectrum of {(μ4-TCNE)[Fe(CO)2(C5H5)]4}3+ which shows four equiv. [Fe(CO)2(C5H5)]+ moieties through 57Fe and 13C(CO) hyperfine coupling in nonenriched material. DFT calcns. reproduce the exptl. EPR data. A survey of discrete TCNE and TCNQ complexes [(\textgreek{m}4-TCNX)(MLn)4] exhibits a dichotomy between the systems {(μ4-TCNX)[Fe(CO)2(C5H5)]4}4+ and {(μ4-TCNQ)[Re(CO)3(bpy)]4}4+ with their negligible metal-to-ligand electron transfer and several other compds. of TCNE or TCNQ with Mn, Ru, Os, or Cu complex fragments which display evidence for a strong such interaction, i.e., an appreciable value \textgreek{d} in the formulation {(μ4-TCNXδ-)[Mx+δ/4Ln]4}. Irreversibility of the 1st redn. of {(μ4-TCNB)[Fe(CO)2(C5H5)]4}(BF4)4 precluded spectroelectrochem. studies; however, the high-energy CN stretching frequencies and charge transfer absorptions of that TCNB analog also confirm the exceptional position of {(μ4-TCNX)[Fe(CO)2(C5H5)]4}(BF4)4. [on SciFinder(R)]