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



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ID: 683892.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Ancillary Ligand Effects upon Dithiolene Redox Noninnocence in Tungsten Bis(dithiolene) Complexes
Authors:Yan, Yong; Keating, Christopher; Chandrasekaran, Perumalreddy; Jayarathne, Upul; Mague, Joel T.; DeBeer, Serena; Lancaster, Kyle M.; Sproules, Stephen; Rubtsov, Igor V.; Donahue, James P.
Language:English
Date of Publication (YYYY-MM-DD):2013
Title of Journal:Inorganic Chemistry
Journal Abbrev.:Inorg. Chem.
Volume:52
Start Page:6743
End Page:6751
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:An expanded set of compounds of the type [W(S2C2Me2)(2)L1L2](n) (n = 0: L-1 = L-2 = CO, 1; L-1 = L-2 = (CNBu)-Bu-t, 2; L-1 = CO, L-2 = carbene, 3; L-1 = CO, L-2 = phosphine, 4; L-1 = L-2 = phosphine, 5. n = 2-: L-1 = L-2 = CN-, [6](2-)) has been synthesized and characterized. Despite isoelectronic formulations, the compound set reveals gradations in the dithiolene ligand redox level as revealed by intraligand bond lengths, upsilon(CCchelate)) and rising edge energies in the sulfur K-edge X-ray absorption spectra (XAS). Differences among the terminal series members, 1 and [6](2-), are comparable to differences seen in homoleptic dithiolene complexes related by full electron transfer to/from a dithiolene-based MO. The key feature governing these differences is the favorable energy of the tungsten d orbitals and exert an oxidizing effect on both metal and too high in energy to mix effectively with tungsten and thus leave how, and the degree to which, the redox level of a noninnocent CO pi* orbitals, which are suitably positioned to overlap with tungsten d orbitals and exert an oxidizing effect on both metal and dithiolene ligand via pi-backbonding. The CN- pi* orbitals are too high in energy to mix effectively with tungsten and thus leave the filled dithiolene pi* orbitals unperturbed. This work shows how, and the degree to which, the redox level of a noninnocent ligand can be modulated by the choice of ancillary ligands(s).
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:Yan, Y.; Keating, C.; Jayarathne, U.; Mague, J.T.; Rubtsov, I.V.; Donahue, J.P.; Tulane Univ, Dept Chem, New Orleans, LA 70118 USA.
Chandrasekaran, P.; Lamar Univ, Dept Chem & Biochem, Beaumont, TX 77710 USA.;
Sproules, S.;Univ Glasgow, WestCHEM, Sch Chem, Glasgow G12 8QQ, Lanark, Scotland.
Identifiers:ISI:000320015700056 [ID No:1]
ISSN:0020-1669 [ID No:2]
DOI:10.1021/ic4009174
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