Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls
KAUST Grant NumberCHE-0910623
Online Publication Date2013-05-31
Print Publication Date2013-06-17
Permanent link to this recordhttp://hdl.handle.net/10754/598542
MetadataShow full item record
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.
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.
SponsorsOur 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.
PublisherAmerican Chemical Society (ACS)
CollectionsPublications Acknowledging KAUST Support
- SO₂--yet another two-faced ligand.
- Authors: Li J, Rogachev AY
- Issue date: 2015 Jan 21
- The (Dioximate)Ni<sup>II</sup>/I<sub>2</sub> System: Ligand Oxidation and Binding Modes of Triiodide Species.
- Authors: Efimenko ZM, Novikov AS, Ivanov DM, Piskunov AV, Vereshchagin AA, Levin OV, Bokach NA, Kukushkin VY
- Issue date: 2020 Feb 17
- Borylene complexes (BH)L2 and nitrogen cation complexes (N+)L2: isoelectronic homologues of carbones CL2.
- Authors: Celik MA, Sure R, Klein S, Kinjo R, Bertrand G, Frenking G
- Issue date: 2012 Apr 27
- Evidence for the involvement of 5f orbitals in the bonding and reactivity of organometallic actinide compounds: thorium(IV) and uranium(IV) bis(hydrazonato) complexes.
- Authors: Cantat T, Graves CR, Jantunen KC, Burns CJ, Scott BL, Schelter EJ, Morris DE, Hay PJ, Kiplinger JL
- Issue date: 2008 Dec 24
- A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.
- Authors: De La Cruz C, Sheppard N
- Issue date: 2011 Jan