Investigation of the iron–carbon bonding for alkyl, alkynyl, carbene, vinylidene, and allenylidene complexes using 57Fe Mössbauer spectroscopy

Guillaume, Valérie; Thominot, Patrice; Coat, Françoise; Mari, Alain; Lapinte, Claude

doi:10.1016/s0022-328x(98)00444-6

Cited by 71 publications

(88 citation statements)

References 46 publications

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“…5 for 13 + [PF 6 ]. The spectroscopic characteristics of these doublets are very close to those obtained for mononuclear Fe(II) and Fe(III) complexes indicating the localization of the electronic spin on the slow time scale of Mö ssbauer spectroscopy [73].…”

Section: Bis(iron) Systems With Localized MV Statessupporting

confidence: 71%

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Lapinte

2008

Journal of Organometallic Chemistry

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Section: Bis(iron) Systems With Localized MV Statessupporting

confidence: 71%

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Lapinte

2008

Journal of Organometallic Chemistry

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“…The quadrupolar splitting and isotopic shift obtained from the Mçssbauer spectrum of the isolated sample is nevertheless suggestive of the presence of a Fe IIIalkynyl species that is distinct from 2A C H T U N G T R E N N U N G [PF 6 ] ( Table 5). [23] Finally, the infrared spectrum of the solid sample reveals a new absorption at 1944 cm À1 , which could correspond to one of the new n CC stretches expected for…”

Section: Optical Electron Transfer In 3-mentioning

confidence: 82%

“…The Mçssbauer spectrum reveals the presence of a new Fe III species with an isotopic shift different to that of 3-HA C H T U N G T R E N N U N G [PF 6 ] (Table 3). [23] DFT computations: Density functional theory (DFT) calculations were performed on the dinuclear Fe II /Ru II complex 3-H and on its mono-and dioxidized states (3-H + and 3-H 2 + , respectively) to obtain further information about their electronic structures and their physical properties (see Computational Details in the Experimental Section). Singlet diamagnetic, broken symmetry (BS), and triplet (T) spin states were considered for the dication 3-H 2 + .…”

Section: Optical Electron Transfer In 3-mentioning

confidence: 99%

Electron‐Rich Iron/Ruthenium Arylalkynyl Complexes for Third‐Order Nonlinear Optics: Redox‐Switching between Three States

Gauthier

Argouarch

Paul

et al. 2011

Chemistry A European J

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The new [(η(2)-dppe)(η(5)-C(5)Me(5))Fe(C≡C-1,4-C(6)H(4)C≡C)Ru(η(2) -dppe)(2) C≡C(C(6)H(5))] complex (3-H) and its hexanuclear relative [{(η(2)-dppe)(η(5)-C(5) Me(5))Fe(C≡C-1,4-C(6)H(4)-C≡C)Ru(η(2)-dppe)(2)(C≡C-1,4-C(6)H(4)C≡C)(3)(1,3,5-C(6)H(3))] (4) have been synthesized and characterized. The linear and cubic nonlinear optical properties of these compounds in their various redox states have been studied along with those of the analogous complexes [(η(2)-dppe)(η(5)-C(5)Me(5))Fe(C≡C-1,4-C(6)H(4)C≡C)Ru(η(2)-dppe)(2)R][PF(6)](n) (n=0-2; R=Cl, 2-Cl; R=C≡C(4-C(6)H(4)NO(2)),3-NO(2)). We show that molecules exhibiting large third-order nonlinearities can be obtained by assembling such dinuclear Fe/Ru units around a central 1,3,5-substituted C(6)H(3) core. These data are discussed with a particular emphasis on the large changes in their nonlinear (third-order) optical properties brought about by oxidation. Experimental and computational (DFT) evidence for the electronic structures of these compounds in their various redox states is presented using 3-H(n+) as a prototypical model. Single crystals of this complex in its mono-oxidized state (3-H[PF(6)]) provide the first structural data for such carbon-rich Fe(III) /Ru(II) heteronuclear mixed-valent (MV) systems. Although experimental evidence for the structure of the dioxidized states was more difficult to obtain, the theoretical study reveals that 3-H(2+) can be considered to have a biradical structure with two independent spins. The low-lying absorptions that appear in the near-infrared (NIR) range for all these compounds following oxidation correspond to intervalence charge-transfer (IVCT) bands for the mono-oxidized states and to ligand-to-metal charge-transfer (LMCT) transitions for the dioxidized states. These play a crucial role in the strong optical modulation achieved. The possibility of accessing additional states with distinct linear or nonlinear optical properties is also briefly discussed.

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“…[7] Characteristic attributes of allenylidene complexes include: (i) the asymmetric valence band known as the ''allenylidene stretch'', giving rise to highly intense absorption bands in their infrared spectra, (ii) low-field signals for the carbon atoms of the unsaturated ligands in their 13 C NMR spectra, [4,8] and (iii) their optical spectra, which feature two bands in the visible region. The band at lower energy is due to the forbidden HOMO Ǟ LUMO transition and so is only weak, while that at higher energy is much more intense and represents the allowed transition from the lower lying second-highest occupied molecular orbital HOMO-1.…”

Section: )]mentioning

confidence: 99%

(Allenylidene)ruthenium Complexes with Redox‐Active Substituents and Ligands

et al. 2003

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, L 2 = 2 PPh 3 or 1,1Ј-bis(diphenylphosphanyl)ferrocene (dppf), R = Ph or ferrocenyl] and their spectroscopic and electrochemical characteristics. Three of these compounds possess redox-active, ferrocenebased substituents or ligands − that are oxidized at lower potentials than the ruthenium center itself − attached either to the terminal carbon atom of the allenylidene ligand or to the ruthenium atom. The Fc/Ph-substituted complexes 3a and 3b provide unique examples of hindered rotation of the allenylidene substituent around the M=C bond. For 3a (L 2 = 2 PPh 3 ), two isomers differing in the orientation of the vertically aligned, unsymmetrically substituted allenylidene ligand are discernible even at 388 K. The dppf-substituted congener 3b has the allenylidene ligand in a horizontal orientation and exhibits a rotational barrier, as determined by dynamic 31 P NMR spectroscopy, of ∆G ϶ = 47 kJ/mol at T C = 238 K. The changes in the spectroscopic and electrochemical properties upon replacement of the PPh 3 by a dppf ligand and the Ph by an Fc moiety can be explained in terms of the bonding within these systems. These effects are attenuated when the ferrocene-based redox tags are oxidized, as shown by IR and

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Investigation of the iron–carbon bonding for alkyl, alkynyl, carbene, vinylidene, and allenylidene complexes using 57Fe Mössbauer spectroscopy

Cited by 71 publications

References 46 publications

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Electron‐Rich Iron/Ruthenium Arylalkynyl Complexes for Third‐Order Nonlinear Optics: Redox‐Switching between Three States

(Allenylidene)ruthenium Complexes with Redox‐Active Substituents and Ligands

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