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  Molecular and Electronic Structure of Square-Planar Gold Complexes Containing Two 1,2-Di(4-tert-butylphenyl)ethylene-1,2-dithiolato Ligands:  [Au(2L)2]1+/0/1-/2-. A Combined Experimental and Computational Study

Kokatam, S., Ray, K., Pap, J., Bill, E., Geiger, W. E., LeSuer, R. J., et al. (2007). Molecular and Electronic Structure of Square-Planar Gold Complexes Containing Two 1,2-Di(4-tert-butylphenyl)ethylene-1,2-dithiolato Ligands:  [Au(2L)2]1+/0/1-/2-. A Combined Experimental and Computational Study. Inorganic Chemistry, 46(4), 1100-1111. doi:10.1021/ic061181u.

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Kokatam, Swarnalatha1, Author           
Ray, Kallol1, Author           
Pap, Joseph1, Author           
Bill, Eckhard1, Author           
Geiger, William E.2, Author
LeSuer, Robert J.2, Author
Rieger, Philip H.3, Author
Weyhermüller, Thomas1, Author           
Neese, Frank1, Author           
Wieghardt, Karl1, Author           
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2Department of Chemistry, University of Vermont, Burlington, Vermont 05405, ou_persistent22              
3Department of Chemistry, Brown University , Providence, Rhode Island 02912, ou_persistent22              

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 Abstract: From the reaction of in situ generated 1,2-di(4-tert-butylphenyl)ethylene-1,2-dithiol, 2LH2, and Na[AuCl4]·2H2O in 1,4-dioxane, green brown crystals of diamagnetic [N(n-Bu)4][AuIII(2L)2] (1) were obtained. As shown by cyclic voltammetry, 1 is a member of an electron-transfer series comprising the dianion [AuII(2L)2]2-, the monoanion [AuIII(2L)2]-, the neutral species [AuIII(2L)(2L)]0 ↔ [AuIII(2L)(2L)]0, and the monocation [AuIII(2L)2]+. (2L)1- represents the π radical anion (Srad = 1/2) of the one-electron oxidized closed-shell dianion (2L)2-. Oxidation of 1 in CH2Cl2 with ferrocenium hexafluorophosphate affords green, paramagnetic microcrystals of [AuIII(2L)(2L)] ↔ [AuIII(2L)(2L)] (2) (S = 1/2). Complexes 1 and 2 have been characterized by X-ray crystallography. Both species possess square-planar monoanions and neutral molecules, respectively. From the oxidation reaction of 1 or [N(n-Bu)4][AuIII(3L)2] with 2−3 equiv of [NO]BF4 in CH2Cl2, a green solution of [AuIII(2L)2]+ and green microcrystals of [AuIII(3L)2]BF4 (3) were obtained, respectively; (3L)2- represents the dianion 1,2-di(4-diphenyl)ethylene-1,2-dithiolate, and (3L)1- is its π radical monoanion. The electronic structures of this series of gold species have been elucidated by UV−vis, EPR spectroscopies, and DFT calculations. It is shown computationally by density functional theoretical (DFT) methods that the electronic structure of [AuIII(1L)2]+ is best described as a singlet diradical (St = 0); the ligand mixed valency in the neutral species 2 is of class (III) (delocalized); the monoanion in 1 contains a AuIII ion and two closed-shell dianionic ligands; and the corresponding dianions [Au(L)2]2- are best described as an intermediate AuII/AuIII species with a metal−ligand delocalized SOMO (25% Au 5d, 75% 3p of four S atoms). (1L)2- is the dianion 1,2-di(phenyl)ethylene-1,2-dithiolate, and (1L)1- is the π radical monoanion. The neutral species [PdII(2L)2] (4) has also been synthesized and characterized by X-ray crystallography. Its electronic structure is the same as described for [AuIII(1L)2]+ (singlet diradical), whereas that of the monoanion [PdII(2L)(2L)]- ↔ [Pd(2L)(2L)]- corresponds to that of the neutral gold complex 2. Anodic oxidation of the analogous monoanion [AuIII(mnt)2]-, where mnt = maleonitriledithiolate, gave the neutral complex [Au(mnt)(mnt)] (E1/2 = 0.91 V vs Fc+/Fc). The optical and EPR spectroscopies of [Au(mnt)(mnt)] were consistent with those observed for the corresponding di(tert-butylphenyl)ethylenedithiolate complex 2.

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Language(s): eng - English
 Dates: 2006-06-282007-01-192007-02-19
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic061181u
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 46 (4) Sequence Number: - Start / End Page: 1100 - 1111 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669