Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo2Cp2(μ-SMe)2(μ-X)(μ-Y)] (X=PPh2, Y=Cl; X=SCH3, Y=Br, I): Electrochemical and structural comparisons – The X-ray structure of [{Mo2Cp2Br(μ-O)(μ-SMe)2}2(μ-MoO4)]
| Autor: | François Y. Pétillon, Jean Talarmin, Philippe Schollhammer, Christine Le Roy, Kenneth W. Muir |
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| Přispěvatelé: | Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), University of Glasgow |
| Rok vydání: | 2006 |
| Předmět: |
Dinuclear complexes
Stereochemistry chemistry.chemical_element Halide Crystal structure [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry Electrochemistry 01 natural sciences Biochemistry Inorganic Chemistry chemistry.chemical_compound Cyclopentadienyl complex Oxo ligand [CHIM.CRIS]Chemical Sciences/Cristallography Materials Chemistry [CHIM]Chemical Sciences [CHIM.COOR]Chemical Sciences/Coordination chemistry Cyclopentadienyl Physical and Theoretical Chemistry Acetonitrile Molybdenum 010405 organic chemistry Chemistry Organic Chemistry X-ray 0104 chemical sciences Bromo and iodo bridges Electrochemical behaviour Crystallography Cyclic voltammetry Thiolate |
| Zdroj: | Journal of Organometallic Chemistry Journal of Organometallic Chemistry, Elsevier, 2006, 691 (5), pp.898-906. ⟨10.1016/j.jorganchem.2005.10.033⟩ |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2005.10.033 |
| Popis: | Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo 2 Cp 2 (μ-SMe) 2 (μ-X)(μ-Y)] (X = PPh 2 , Y = Cl ( 1 ); X = SCH 3 , Y = Br ( 3 ), I( 4 )) have been studied. Syntheses and X-ray structures of the new bromo and iodo analogues of [Mo 2 Cp 2 (μ-SMe) 3 (μ-Cl)] ( 2 ) are reported. While preparing 3 a side-product 5 was obtained and structurally characterised as the Mo 5 system [{Mo 2 Cp 2 Br(μ-O)(μ-SMe) 2 } 2 (μ-MoO 4 )], containing a {Mo IV –Mo IV –O–(Mo VI O 2 )–O–Mo IV –Mo IV } unit. The influence of the bridging groups on the structures and electrochemical behaviour of the complexes [Mo 2 Cp 2 (μ-SMe) 2 (μ-X)(μ-Y)] 1 – 4 has been investigated. In MeCN–[NBu 4 ][PF 6 ] the first oxidation of [Mo 2 Cp 2 (μ-SMe) 2 (μ-PPh 2 )(μ-Cl)] ( 1 ) is quasi-reversible, contrasting with the essentially irreversible first oxidation of the thiolate analogue [Mo 2 Cp 2 (μ-SMe) 3 (μ-Cl)] ( 2 ) under similar conditions. The effects of lowering the temperature or increasing the scan rate on the oxidation of 1 were examined: the initial quasi-reversible oxidation at first became irreversible but at still higher scan rates or lower temperatures the oxidation was again quasi-reversible. This suggests that the oxidation of 1 in MeCN is followed by reversible coordination of acetonitrile to afford the species [Mo 2 Cp 2 (μ-SMe) 2 (μ-PPh 2 )(Cl)(MeCN)] + ( 7 + ). Cyclic voltammetry of [Mo 2 Cp 2 (μ-SMe) 3 (μ-Y)](Y = Br ( 3 ) or I ( 4 )) showed two quasi-reversible diffusion-controlled oxidation steps in CH 2 Cl 2 –[NBu 4 ][PF 6 ] or thf–[NBu 4 ][PF 6 ]. In acetonitrile, the fast loss of the halide ligands results in the formation of [Mo 2 Cp 2 (μ-SMe) 3 (MeCN) 2 ] + species. |
| Databáze: | OpenAIRE |
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