Spectroscopic and electrochemical observation of both 17- and 19-electron states of an inorganometallic transition metal complex: [FeIII(η5-C5Me5)(S2CNMe2)2]

Delville-Desbois, Marie-Hélène; Varret, F.; Astruc, Didier

doi:10.1039/c39950000249

Cited by 2 publications

(1 citation statement)

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“…Transition metal complexes with a 17-electron configuration continue to present considerable interest in both fundamental and applied chemistry [1][2][3][4]. These species are invoked as intermediates in many syntheses; some of them, for example, have been proposed as catalysts for olefin metathetical polymerization [5], while metal-centred radicals derived from carbonyl complexes, are frequently used for their exceptional substitutional lability [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Sidorenkova

Berclaz

Ndiaye

et al. 2009

Journal of Physics and Chemistry of Solids

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a b s t r a c tA radical species characterized by a large g-anisotropy and a clearly resolved hyperfine structure with 95/97 Mo and 31 P nuclei is formed, at 77 K, by radiolysis of a single crystal of Mo(CO) 5 PPh 3 . The corresponding EPR signals disappear irreversibly with increasing temperature and the angular dependence of the various coupling constants imply a spin delocalization of $60% and $4% on the molybdenum and the phosphorus atoms, respectively and are, a priori, consistent with the trapping of a one-electron deficient centre. The ability of DFT to predict the EPR tensors for a 17-electron Mo (I) species is verified by calculating the g-tensor and the various 14 N and 13 C coupling tensors previously reported by Hayes for [Mo(CN) 5 NO] 3À . Calculations at the B3LYP/ZORA/SOMF level of theory show that, in contrast to Mo(CO) 5 PH 3 , one-electron oxidation of Mo(CO) 5 PPh 3 causes an appreciable change in the geometry of the complex. The g-tensor and the 95/97 Mo and 31 P isotropic and anisotropic coupling constants calculated for [Mo(CO) 5 PPh 3 ] + Á confirm the trapping of this species in the irradiated crystal of Mo(CO) 5 PPh 3 ; they also show that the conformational modifications induced by the electron release are probably hindered by the nearby complexes.

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Section: Introductionmentioning

confidence: 99%

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Sidorenkova

Berclaz

Ndiaye

et al. 2009

Journal of Physics and Chemistry of Solids

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Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl α-Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO)₃(α-Diimine)Cl and Related Compounds

et al. 2008

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The oxidative electrochemistry of luminescent rhenium (I) complexes of the type Re(CO) 3(LL)Cl, 1, and Re(CO) 3(LL)Br, 2, where LL is an alpha-diimine, was re-examined in acetonitrile. These compounds undergo metal-based one-electron oxidations, the products of which undergo rapid chemical reaction. Cyclic voltammetry results imply that the electrogenerated rhenium (II) species 1 ( + ) and 2 ( + ) disproportionate, yielding [Re(CO) 3(LL)(CH 3CN)] (+), 7, and additional products. Double potential step chronocoulometry experiments confirm that 1 ( + ) and 2 ( + ) react via second-order processes and, furthermore, indicate that the rate of disproportionation is influenced by the basicity and steric requirements of the alpha-diimine ligands. The simultaneous generation of rhenium (I) and (III) carbonyl products was detected upon the bulk oxidation of 1 using infrared spectroelectrochemistry. The rhenium (III) products are assigned as [Re(CO) 3(LL)Cl 2] (+), 5; an inner-sphere electron-transfer mechanism of the disproportionation is proposed on the basis of the apparent chloride transfer. Chemically irreversible two-electron reduction of 5 yields 1 and Cl (-). No direct spectroscopic evidence was obtained for the generation of rhenium (III) tricarbonyl bromide disproportionation products, [Re(CO) 3(LL)Br 2] (+), 6; this is attributed to their relatively rapid decomposition to 7 and dibromine. In addition, the 17-electron radical cations, 7 ( + ), were successfully characterized using infrared spectroelectrochemistry.

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Spectroscopic and electrochemical observation of both 17- and 19-electron states of an inorganometallic transition metal complex: [Fe^III(η⁵-C₅Me₅)(S₂CNMe₂)₂]

Cited by 2 publications

References 20 publications

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl α-Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO)₃(α-Diimine)Cl and Related Compounds

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Spectroscopic and electrochemical observation of both 17- and 19-electron states of an inorganometallic transition metal complex: [FeIII(η5-C5Me5)(S2CNMe2)2]

Cited by 2 publications

References 20 publications

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl α-Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO)3(α-Diimine)Cl and Related Compounds

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Spectroscopic and electrochemical observation of both 17- and 19-electron states of an inorganometallic transition metal complex: [Fe^III(η⁵-C₅Me₅)(S₂CNMe₂)₂]

Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl α-Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO)₃(α-Diimine)Cl and Related Compounds