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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 713857.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Electronic Structure of Ni2E2 Complexes (E = S, Se, Te) and a Global Analysis of M2E2 Compounds: A Case for Quantized E2n- Oxidation Levels with n=2, 3, or 4
Authors:Yao, Shu A.; Martin-Diaconescu, Vlad; Infante, Ivan; Lancaster, Kyle M.; Götz, Andreas W.; DeBeer, Serena; Berry, John F.
Language:English
Date of Publication (YYYY-MM-DD):2015
Title of Journal:Journal of the American Chemical Society
Journal Abbrev.:J.Am.Chem.Soc.
Volume:137
Issue / Number:15
Start Page:4993
End Page:5011
Review Status:Internal review
Audience:Experts Only
Abstract / Description:The diamagnetic compounds Cp'2Ni2E2 (1: E = S, 2: E = Se, 3: E = Te; Cp' = 1,2,3,4,-tetraisopropylcyclopentadienyl), first reported by Sitzmann and co-workers in 2001 [Sitzmann, H.; Saurenz, D.; Wolmershauser, G.; Klein, A.; Boese, R. Organometallics 2001, 20, 700], have unusual E center dot center dot center dot E distances, leading to ambiguities in how to best describe their electronic structure. Three limiting possibilities are considered: case A, in which the compounds contain singly bonded E-2(2)- units; case B, in which a three-electron E-E half-bond exists in a formal E-2(3-) unit; case C, in which two E-2(-) ions exist with no formal E-E bond. One-electron reduction of 1 and 2 yields the new compounds [Cp*Co-2][Cp'2Ni2E2] (1red: E = S, 2red: E = Se; Cp* = 1,2,3,4,5-pentamethylcyclopentadieyl). Evidence from X-ray crystallography, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy suggest that reduction of 1 and 2 is Ni-centered. Density functional theory (DFT) and ab initio multireference methods (CASSCF) have been used to investigate the electronic structures of 1-3 and indicate covalent bonding of an E23- ligand with a mixed-valent Ni-2(II,III) species. Thus, reduction of 1 and 2 yields Ni2(II,II) species 1red and 2red that bear unchanged E-2(3-) ligands. We provide strong computational and experimental evidence, including results from a large survey of data from the Cambridge Structural Database, indicating that M2E2 compounds occur in quantized E-2 oxidation states of (2 x E2-), E-2(3-), and E-2(2-), rather than displaying a continuum of variable E-E bonding interactions.
Comment of the Author/Creator:Date: 2015, APR 22 2015
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Yao,S.A.; Berry,J.F.] Univ Wisconsin, Dept.Chem., Madison, WI 53706 USA.
[Infante,I.; ] Euskal Herriko Unibertsitatea, Kimika Fak, Donostia San Sebastian 20080, Euskadi, Spain
[Lancaster,K.M.;] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
[Gotz,A.W.; ] Univ Calif San Diego, San Diego Supercomp Ctr, La Jolla, CA 92093 USA] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
Identifiers:ISI:000353606700030 [ID No:1]
ISSN:0002-7863 [ID No:2]
DOI:10.1021/ja511607j [ID No:3]
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