Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls

Handle URI:
http://hdl.handle.net/10754/598542
Title:
Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls
Authors:
Rogachev, Andrey Yu.; Hoffmann, Roald
Abstract:
Just a couple of transition metal complexes of the familiar triiodide anion are known. To investigate the bonding in these, as well as isomeric possibilities, we examined theoretically adducts of I3 - with model organometallic fragments, [Cr(CO)5] and [Mn(CO) 5]+. Bonding energy computations were augmented by a Natural Bond Orbital (NBO) perturbation theory analysis and Energy Decomposition Analysis (EDA). The bonding between I3 - and the organometallic fragment is substantial, especially for the electrostatically driven anion-cation case. "End-on" coordination is favored by 5-13 kcal/mol over "side-on" (to the central I of I3 -), with a ∼10 kcal/mol barrier for isomerization. A developing asymmetry in the I-I bonding of "end-on" coordinated I 3 - led us to consider in some detail the obvious fragmentation to a coordinated I- and free I2. While the signs of incipient fragmentation in that direction are there, these is a definite advantage to maintaining some I- to I2 bonding in triiodide complexes. © 2013 American Chemical Society.
Citation:
Rogachev AY, Hoffmann R (2013) Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls . Inorg Chem 52: 7161–7171. Available: http://dx.doi.org/10.1021/ic400772u.
Publisher:
American Chemical Society (ACS)
Journal:
Inorganic Chemistry
Issue Date:
17-Jun-2013
DOI:
10.1021/ic400772u
PubMed ID:
23725645
Type:
Article
ISSN:
0020-1669; 1520-510X
Sponsors:
Our work was supported by the National Science Foundation, Research Grant CHE-0910623. Computational facilities provided by KAUST (King Abdullah University of Science and Technology) Supercomputing Laboratory are gratefully acknowledged.
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Full metadata record

DC FieldValue Language
dc.contributor.authorRogachev, Andrey Yu.en
dc.contributor.authorHoffmann, Roalden
dc.date.accessioned2016-02-25T13:31:52Zen
dc.date.available2016-02-25T13:31:52Zen
dc.date.issued2013-06-17en
dc.identifier.citationRogachev AY, Hoffmann R (2013) Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls . Inorg Chem 52: 7161–7171. Available: http://dx.doi.org/10.1021/ic400772u.en
dc.identifier.issn0020-1669en
dc.identifier.issn1520-510Xen
dc.identifier.pmid23725645en
dc.identifier.doi10.1021/ic400772uen
dc.identifier.urihttp://hdl.handle.net/10754/598542en
dc.description.abstractJust a couple of transition metal complexes of the familiar triiodide anion are known. To investigate the bonding in these, as well as isomeric possibilities, we examined theoretically adducts of I3 - with model organometallic fragments, [Cr(CO)5] and [Mn(CO) 5]+. Bonding energy computations were augmented by a Natural Bond Orbital (NBO) perturbation theory analysis and Energy Decomposition Analysis (EDA). The bonding between I3 - and the organometallic fragment is substantial, especially for the electrostatically driven anion-cation case. "End-on" coordination is favored by 5-13 kcal/mol over "side-on" (to the central I of I3 -), with a ∼10 kcal/mol barrier for isomerization. A developing asymmetry in the I-I bonding of "end-on" coordinated I 3 - led us to consider in some detail the obvious fragmentation to a coordinated I- and free I2. While the signs of incipient fragmentation in that direction are there, these is a definite advantage to maintaining some I- to I2 bonding in triiodide complexes. © 2013 American Chemical Society.en
dc.description.sponsorshipOur work was supported by the National Science Foundation, Research Grant CHE-0910623. Computational facilities provided by KAUST (King Abdullah University of Science and Technology) Supercomputing Laboratory are gratefully acknowledged.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleHypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonylsen
dc.typeArticleen
dc.identifier.journalInorganic Chemistryen
dc.contributor.institutionCornell University, Ithaca, United Statesen
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