On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen, Ni(N2)2
Identifieur interne : 000115 ( France/Analysis ); précédent : 000114; suivant : 000116On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen, Ni(N2)2
Auteurs : Olaf Hübner ; Laurent Manceron [France] ; Hans-Jörg Himmel [Allemagne]Source :
- Chemistry – A European Journal [ 0947-6539 ] ; 2014-12-15.
Abstract
The electronic ground and excited states of the coordinatively unsaturated complex Ni(η1‐N2)2, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η1‐N2)2 with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2, with one and two side‐on coordinated dinitrogen ligands, respectively.
Unsaturated and photolabile: The vibrational spectra and electronic structure of the bis‐dinitrogen complex Ni(N2)2 are studied in detail, and the end‐on bonded complex Ni(η1‐N2)2 is found to photoisomerize to Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2 with one and two side‐on bonded dinitrogen ligands, respectively (see figure).
Url:
DOI: 10.1002/chem.201402824
Affiliations:
Links toward previous steps (curation, corpus...)
- to stream Istex, to step Corpus: 001158
- to stream Istex, to step Curation: 001158
- to stream Istex, to step Checkpoint: 000030
- to stream Main, to step Merge: 000767
- to stream Main, to step Curation: 000766
- to stream Main, to step Exploration: 000766
- to stream France, to step Extraction: 000115
Links to Exploration step
ISTEX:E3849FBE2D48671D9AE0D6091AB299EF4018E843Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen, Ni(N2)2</title><author><name sortKey="Hubner, Olaf" sort="Hubner, Olaf" uniqKey="Hubner O" first="Olaf" last="Hübner">Olaf Hübner</name></author><author><name sortKey="Manceron, Laurent" sort="Manceron, Laurent" uniqKey="Manceron L" first="Laurent" last="Manceron">Laurent Manceron</name></author><author><name sortKey="Himmel, Hans Rg" sort="Himmel, Hans Rg" uniqKey="Himmel H" first="Hans-Jörg" last="Himmel">Hans-Jörg Himmel</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:E3849FBE2D48671D9AE0D6091AB299EF4018E843</idno><date when="2014" year="2014">2014</date><idno type="doi">10.1002/chem.201402824</idno><idno type="url">https://api.istex.fr/ark:/67375/WNG-CXZ3GH5V-F/fulltext.pdf</idno><idno type="wicri:Area/Istex/Corpus">001158</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">001158</idno><idno type="wicri:Area/Istex/Curation">001158</idno><idno type="wicri:Area/Istex/Checkpoint">000030</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Checkpoint">000030</idno><idno type="wicri:doubleKey">0947-6539:2014:Hubner O:on:the:electronic</idno><idno type="wicri:Area/Main/Merge">000767</idno><idno type="wicri:Area/Main/Curation">000766</idno><idno type="wicri:Area/Main/Exploration">000766</idno><idno type="wicri:Area/France/Extraction">000115</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main">On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen, Ni(N2)2</title><author><name sortKey="Hubner, Olaf" sort="Hubner, Olaf" uniqKey="Hubner O" first="Olaf" last="Hübner">Olaf Hübner</name><affiliation><wicri:noCountry code="subField">(+49) 6221‐545707</wicri:noCountry></affiliation></author><author><name sortKey="Manceron, Laurent" sort="Manceron, Laurent" uniqKey="Manceron L" first="Laurent" last="Manceron">Laurent Manceron</name><affiliation wicri:level="1"><country xml:lang="fr">France</country><wicri:regionArea>Synchrotron Soleil, AILES Beamline, 91192 Saint Aubin (France) and CNRS‐MONARIS UMR 8233, 4 Place Jussieu</wicri:regionArea><wicri:noRegion>4 Place Jussieu</wicri:noRegion><wicri:noRegion>4 Place Jussieu</wicri:noRegion></affiliation></author><author><name sortKey="Himmel, Hans Rg" sort="Himmel, Hans Rg" uniqKey="Himmel H" first="Hans-Jörg" last="Himmel">Hans-Jörg Himmel</name><affiliation></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Allemagne</country></affiliation><affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Chemistry – A European Journal</title><title level="j" type="alt">CHEMISTRY - A EUROPEAN JOURNAL</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><biblScope unit="vol">20</biblScope><biblScope unit="issue">51</biblScope><biblScope unit="page" from="17025">17025</biblScope><biblScope unit="page" to="17038">17038</biblScope><biblScope unit="page-count">14</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2014-12-15">2014-12-15</date></imprint><idno type="ISSN">0947-6539</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The electronic ground and excited states of the coordinatively unsaturated complex Ni(η1‐N2)2, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η1‐N2)2 with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2, with one and two side‐on coordinated dinitrogen ligands, respectively.</div><div type="abstract" xml:lang="en">Unsaturated and photolabile: The vibrational spectra and electronic structure of the bis‐dinitrogen complex Ni(N2)2 are studied in detail, and the end‐on bonded complex Ni(η1‐N2)2 is found to photoisomerize to Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2 with one and two side‐on bonded dinitrogen ligands, respectively (see figure).</div></front></TEI><affiliations><list><country><li>Allemagne</li><li>France</li></country></list><tree><noCountry><name sortKey="Hubner, Olaf" sort="Hubner, Olaf" uniqKey="Hubner O" first="Olaf" last="Hübner">Olaf Hübner</name></noCountry><country name="France"><noRegion><name sortKey="Manceron, Laurent" sort="Manceron, Laurent" uniqKey="Manceron L" first="Laurent" last="Manceron">Laurent Manceron</name></noRegion></country><country name="Allemagne"><noRegion><name sortKey="Himmel, Hans Rg" sort="Himmel, Hans Rg" uniqKey="Himmel H" first="Hans-Jörg" last="Himmel">Hans-Jörg Himmel</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Sante/explor/H2N2V1/Data/France/Analysis
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000115 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/France/Analysis/biblio.hfd -nk 000115 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Sante
|area= H2N2V1
|flux= France
|étape= Analysis
|type= RBID
|clé= ISTEX:E3849FBE2D48671D9AE0D6091AB299EF4018E843
|texte= On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen, Ni(N2)2
}}
| This area was generated with Dilib version V0.6.33. |  |