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  The Rhenium Tris(dithiolene) Electron Transfer Series: Calibrating Covalency

Sproules, S., Weyhermüller, T., Goddard, R., & Wieghard, K. (2011). The Rhenium Tris(dithiolene) Electron Transfer Series: Calibrating Covalency. Inorganic Chemistry, 50(24), 12623-12631. doi:10.1021/ic2016534.

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Sproules, Stephen1, 2, Autor
Weyhermüller, Thomas1, Autor
Goddard, Richard3, Autor           
Wieghard, Karl1, Autor
Affiliations:
1Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany, ou_persistent13              
2EPSRC National UK EPR Facility and Service, Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K., ou_persistent22              
3Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 Zusammenfassung: Four members of the rhenium tris(dithiolene) electron transfer series have been prepared, [Re(S2C2R2)3]z {R = Ph, z = 1+ (1), 0 (2), 1– (3); R = CN, z = 2– (4)}, with the anions in 3 and 4 structurally characterized. The intraligand C–S and C–C bond lengths for 3 vs 2 are indicative of ligand reduction concomitant with an overall distorted trigonal prismatic geometry (Θ = 26.3° cf. 3.8° in 2). The distorted octahedral ReS6 polyhedron in 4 (Θ = 38.3°) indicates reduction of the metal to a Re(IV) d3 central ion. This series has been probed by sulfur K-edge X-ray absorption spectroscopy (XAS), and the electronic structures are unambiguously defined as follows: [ReV(L34–)]1+ (S = 0) for the monocation in 1; [ReV(L35–•)]0 (S = 1/2) for neutral 2; [ReV(L36–)]1– (S = 0) for the monoanion in 3; and [ReIV(L36–)]2– (S = 1/2) for the dianion in 4. The sulfur 3p character in the frontier orbitals—the covalency—is estimated by two different approaches. Method A utilizes the radial dipole integral (Is) derived from the S 1s → 4p transition, whereas method B, involves time-dependent density functional theoretical (TD-DFT) calculation of the pre-edge transitions and calibrated to the intensity in [Re(pdt)3] (pdt2– = 1,2-diphenyl-1,2-dithiolate). The two estimates are contrasted for the rhenium series and extended to the [V(pdt)3]0/1–, and [Mo(mdt)3]0/1–/2– (mdt2– = 1,2-dimethyl-1,2-dithiolate) series, ultimately providing a refined description of the contested electronic structure of neutral molybdenum (and tungsten) tris(dithiolenes) compounds.

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Sprache(n): eng - English
 Datum: 2011-08-012011-11-102011-12-19
 Publikationsstatus: Erschienen
 Seiten: 9
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ic2016534
ISI: 000297782200041
 Art des Abschluß: -

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Titel: Inorganic Chemistry
  Kurztitel : Inorg. Chem.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: 9 Band / Heft: 50 (24) Artikelnummer: - Start- / Endseite: 12623 - 12631 Identifikator: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669