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Electronic Structure of Neutral and Monoanionic Tris(benzene-1,2-dithiolato)metal Complexes of Molybdenum and Tungsten.
- Source :
-
Inorganic Chemistry . 7/9/2007, Vol. 46 Issue 14, p5642-5650. 9p. 7 Diagrams, 6 Charts, 6 Graphs. - Publication Year :
- 2007
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Abstract
- The reaction of 3 equiv of the ligand 2-mercapto-3,5-di-tert-butylaniline, H2[LN,S], or 3,5-di-tert-butyl-1,2-benzenedithiol, H2[LS,S], with 1 equiv of [MoO2(acac)2] or WCI6 (acac = acetonylacetate(1-)) in methanol or CCI4 afforded the diamagnetic neutral complexes [MoV(LN,S)2(L*N,S)]0 (1), [MoV(LS,S)2(L*S,S)1 (2), and (WV(LS,S)2(L*S,S)] (3), where (L*N,S)- and (L*S,S)- represent monoanionic π-radical ligands (Srad = 1/2), which are the one-electron oxidized forms of the corresponding closed-shell dianions (LN,S)2- and (LS,S)2-. Complexes 1-3 are trigonal-prismatic members of the electron-transfer series [ML3]z (z = 0, 1-, 2-). Reaction of 2 and 3 with [N(n-Bu)4](SH) in CH2Cl2 under anaerobic conditions afforded paramagnetic crystalline [N(n-Bu)4](MoV(LS,S)3] (4) and [N(n-Bu)4][WV(LS,S)3] (5). Complexes 1-5 have been characterized by X-ray crystallography. S K-edge X-ray absorption and infrared spectroscopy prove that a π-radical ligand (L*S,S)- is present in neutral 2 and 3, whereas the monoanions [MV(LS,S)3]- contain only closed-shell dianionic ligands. These neutral species have previously been incorrectly described as [MVI(L)3)0 complexes with a MoVI or WVI (d0) central metal ion; they are, in fact MV (d¹) (M = Mo, W) species: [MoV(LS,S)2(L*S,S)] and [WV(LS,S)2(L*S,S)] with a diamagnetic ground state St = 0, which is generated by intramolecular, antiferromagnetic coupling between the MV (d¹) central ion (SM = 1/2) and a ligand π radical (L*S,S) (Srad = 1/2). [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00201669
- Volume :
- 46
- Issue :
- 14
- Database :
- Academic Search Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 25929622
- Full Text :
- https://doi.org/10.1021/ic700600r