Ring slippage in indenyl complexes: structure and bonding
Identifieur interne : 004525 ( Istex/Curation ); précédent : 004524; suivant : 004526Ring 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.
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DOI: 10.1016/S0010-8545(98)00247-1
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Maria José Calhorda<affiliation><mods:affiliation>Corresponding author. Correspondence address: ITQB, Quinta do Marquês, EAN, Apart. 127, 2781-901 Oeiras, Portugal. Tel.: +351-1-4469451; fax: +351-1-4411277</mods:affiliation>
<wicri:noCountry code="subField">411277</wicri:noCountry>
</affiliation>
<affiliation wicri:level="1"><mods:affiliation>E-mail: mjc@itqb.unl.pt</mods:affiliation>
<country wicri:rule="url">Portugal</country>
</affiliation>
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<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>
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