Ring slippage in indenyl complexes: structure and bonding
Identifieur interne : 008168 ( Main/Exploration ); précédent : 008167; suivant : 008169Ring slippage in indenyl complexes: structure and bonding
Auteurs : Maria José Calhorda [Portugal] ; Lu S F. Veiros [Portugal]Source :
- Coordination Chemistry Reviews [ 0010-8545 ] ; 1998.
English descriptors
Abstract
A review of some structural and reactivity aspects of the coordinated indenyl ligand, dealing mainly with the systems theoretically studied by the authors is presented. In the first section, the structural characterization of η5 and η3 indenyl is attempted, noticing that the nodal properties of the π orbitals of the indenyl prevent a totally symmetric coordination in a η5-indenyl. The two bonds to the hinge carbon atoms are always longer, and the distance becomes longer than a M–C bond in the η3-indenyl derivatives. Some intermediate distances are found in [(Ind)2Ni] where, formally, the ligand is halfway between η5 and η3. The ring slippage occurs when two electrons are added to the system, occupying a metal–indenyl antibonding orbital, which becomes more stable upon folding. We reviewed electrochemical and ligand addition driven slippage, in the second section. A comparison with the behavior of the cyclopentadienyl ligand was attempted in the end.
Url:
DOI: 10.1016/S0010-8545(98)00247-1
Affiliations:
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Veiros</name><affiliation wicri:level="1"><country xml:lang="fr">Portugal</country><wicri:regionArea>CQE, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisbon</wicri:regionArea><wicri:noRegion>1049-001 Lisbon</wicri:noRegion></affiliation></author></analytic><monogr></monogr><series><title level="j">Coordination Chemistry Reviews</title><title level="j" type="abbrev">CCR</title><idno type="ISSN">0010-8545</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998">1998</date><biblScope unit="volume">185–186</biblScope><biblScope unit="supplement">C</biblScope><biblScope unit="page" from="37">37</biblScope><biblScope unit="page" to="51">51</biblScope></imprint><idno type="ISSN">0010-8545</idno></series><idno type="istex">A2963FA12160998036AF2C956546A68BE43F9A66</idno><idno type="DOI">10.1016/S0010-8545(98)00247-1</idno><idno type="PII">S0010-8545(98)00247-1</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0010-8545</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Haptotropic shift</term><term>Indenyl slippage</term><term>Molecular orbital calculations</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A review of some structural and reactivity aspects of the coordinated indenyl ligand, dealing mainly with the systems theoretically studied by the authors is presented. In the first section, the structural characterization of η5 and η3 indenyl is attempted, noticing that the nodal properties of the π orbitals of the indenyl prevent a totally symmetric coordination in a η5-indenyl. The two bonds to the hinge carbon atoms are always longer, and the distance becomes longer than a M–C bond in the η3-indenyl derivatives. Some intermediate distances are found in [(Ind)2Ni] where, formally, the ligand is halfway between η5 and η3. The ring slippage occurs when two electrons are added to the system, occupying a metal–indenyl antibonding orbital, which becomes more stable upon folding. We reviewed electrochemical and ligand addition driven slippage, in the second section. A comparison with the behavior of the cyclopentadienyl ligand was attempted in the end.</div></front></TEI><affiliations><list><country><li>Portugal</li></country></list><tree><country name="Portugal"><noRegion><name sortKey="Calhorda, Maria Jose" sort="Calhorda, Maria Jose" uniqKey="Calhorda M" first="Maria José" last="Calhorda">Maria José Calhorda</name></noRegion><name sortKey="Calhorda, Maria Jose" sort="Calhorda, Maria Jose" uniqKey="Calhorda M" first="Maria José" last="Calhorda">Maria José Calhorda</name><name sortKey="Calhorda, Maria Jose" sort="Calhorda, Maria Jose" uniqKey="Calhorda M" first="Maria José" last="Calhorda">Maria José Calhorda</name><name sortKey="Veiros, Lu S F" sort="Veiros, Lu S F" uniqKey="Veiros L" first="Lu S F." last="Veiros">Lu S F. Veiros</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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