Handle URI:
http://hdl.handle.net/10754/598671
Title:
Iodine (I 2 ) as a Janus-Faced Ligand in Organometallics
Authors:
Rogachev, Andrey Yu.; Hoffmann, Roald
Abstract:
The four known diiodine complexes have distinct geometries. These turn out, as we demonstrate by a bonding analysis, to be a direct consequence of diiodine acting as an acceptor in one set, the van Koten complexes, and as a donor in the Cotton, Dikarev, and Petrukhina extended structure. The primary analytical tool utilized is perturbation theory within the natural bond orbital (NBO) framework, supported by an energy decomposition analysis. The study begins by delineating the difference between canonical molecular orbitals (MOs) and NBOs. When iodine acts as an acceptor, bonding collinearly in the axial position of a square-planar d8 Pt(II) complex, the dominant contributor to the bonding is a σ*(I-I) orbital as the acceptor orbital, while a mainly dz 2 orbital centered on the metal center is the corresponding donor. That this kind of bonding is characteristic of axial bonding in d8 complexes was supported by model calculations with incoming donors and acceptors, NH3 and BH3. In contrast, the distinct "bent" coordination of the I2 bound at the axial position of the [Rh2(O2CCF3)4] paddle-wheel complex is associated with a dominant donation from a p-type lone pair localized on one of two iodine atoms, the σ*(Rh-Rh) antibonding orbital of the metal complex acting as an acceptor orbital. We check the donor capabilities of I2 in some hypothetical complexes with Lewis acids, H+, AlCl3, B(CF3)3. Also, we look at the weakly bound donor-acceptor couple [(I2)·(I2)]. We explore the reasons for the paucity of I2 complexes and propose candidates for synthesis. © 2013 American Chemical Society.
Citation:
Rogachev AY, Hoffmann R (2013) Iodine (I 2 ) as a Janus-Faced Ligand in Organometallics . Journal of the American Chemical Society 135: 3262–3275. Available: http://dx.doi.org/10.1021/ja312584u.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
27-Feb-2013
DOI:
10.1021/ja312584u
PubMed ID:
23384185
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
We are grateful to G. van Koten for bringing to our attention a number of important papers and useful comments, and to P. Wolzanski for steering us to the work of A. Heyduk. 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.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorRogachev, Andrey Yu.en
dc.contributor.authorHoffmann, Roalden
dc.date.accessioned2016-02-25T13:34:11Zen
dc.date.available2016-02-25T13:34:11Zen
dc.date.issued2013-02-27en
dc.identifier.citationRogachev AY, Hoffmann R (2013) Iodine (I 2 ) as a Janus-Faced Ligand in Organometallics . Journal of the American Chemical Society 135: 3262–3275. Available: http://dx.doi.org/10.1021/ja312584u.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.pmid23384185en
dc.identifier.doi10.1021/ja312584uen
dc.identifier.urihttp://hdl.handle.net/10754/598671en
dc.description.abstractThe four known diiodine complexes have distinct geometries. These turn out, as we demonstrate by a bonding analysis, to be a direct consequence of diiodine acting as an acceptor in one set, the van Koten complexes, and as a donor in the Cotton, Dikarev, and Petrukhina extended structure. The primary analytical tool utilized is perturbation theory within the natural bond orbital (NBO) framework, supported by an energy decomposition analysis. The study begins by delineating the difference between canonical molecular orbitals (MOs) and NBOs. When iodine acts as an acceptor, bonding collinearly in the axial position of a square-planar d8 Pt(II) complex, the dominant contributor to the bonding is a σ*(I-I) orbital as the acceptor orbital, while a mainly dz 2 orbital centered on the metal center is the corresponding donor. That this kind of bonding is characteristic of axial bonding in d8 complexes was supported by model calculations with incoming donors and acceptors, NH3 and BH3. In contrast, the distinct "bent" coordination of the I2 bound at the axial position of the [Rh2(O2CCF3)4] paddle-wheel complex is associated with a dominant donation from a p-type lone pair localized on one of two iodine atoms, the σ*(Rh-Rh) antibonding orbital of the metal complex acting as an acceptor orbital. We check the donor capabilities of I2 in some hypothetical complexes with Lewis acids, H+, AlCl3, B(CF3)3. Also, we look at the weakly bound donor-acceptor couple [(I2)·(I2)]. We explore the reasons for the paucity of I2 complexes and propose candidates for synthesis. © 2013 American Chemical Society.en
dc.description.sponsorshipWe are grateful to G. van Koten for bringing to our attention a number of important papers and useful comments, and to P. Wolzanski for steering us to the work of A. Heyduk. 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleIodine (I 2 ) as a Janus-Faced Ligand in Organometallicsen
dc.typeArticleen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionCornell University, Ithaca, United Statesen
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