Source:http://linkedlifedata.com/resource/pubmed/id/15859297
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
4
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| pubmed:dateCreated |
2005-4-29
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| pubmed:abstractText |
Oxidation of the square planar Rh(I) complex [Rh(SPS(Me))(PPh3)] (SPS(Me) = 1-methyl-1-P-2.6-bis(diphenylphosphinosulfide)-3,5-(bisphenyl)-phosphinine) (1) based on mixed SPS-pincer ligand with hexachloroethane yielded the Rh(III) dichloride complex [Rh(SPS(Me))(PPh3)Cl2] (2), which was structurally characterized. The homoleptic Rh(III) complex [Rh(SPS(Me))2][Cl] (4) was obtained via the stoichiometric reaction of SPS(Me) anion (3) with [Rh(tht)3Cl3] (tht = tetrahydrothiophene). Complex 4, which was characterized by X-ray diffraction, was also studied by cyclic voltammetry. Complex 4 can be reversibly reduced at E = -1.16 V (vs SCE) to give the neutral 19-electron Rh(II) complex [Rh(SPS(Me))2] (5). Accordingly, complex 5 could be synthesized via chemical reduction of 4 with zinc dust. EPR spectra of complex 5 were obtained after electrochemical or chemical reduction of 4 in THF or CH2Cl2. Hyperfine interaction with two equivalent 31P nuclei was observed in liquid solution, while an additional coupling with a spin 1/2 nucleus, probably 103Rh, was detected in frozen solution. The 31P couplings are consistent with DFT calculations that predict a drastic increase in the axial P-S bond lengths when reducing (SPS(Me))2Rh(III). In the reduced complex, the unpaired electron is mainly localized in a rhodium d(z2) orbital, consistent with the g-anisotropy measured at 100 K.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Feb
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| pubmed:issn |
0020-1669
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
21
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| pubmed:volume |
44
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
1147-52
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| pubmed:year |
2005
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| pubmed:articleTitle |
Synthesis and X-ray crystal structure of a cationic homoleptic (SPS)2Rh(III) complex and EPR study of its reduction process.
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| pubmed:affiliation |
Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique 91128 Palaiseau Cédex, France.
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| pubmed:publicationType |
Journal Article
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