Structural and electrochemical study of metal carbonyl complexes with chelating bis- and tetrakis(diphenylphosphino)tetrathiafulvalenes

Avarvari, Narcis; Martín, David; Fourmigué, Marc

doi:10.1016/s0022-328x(01)01249-9

Cited by 62 publications

(44 citation statements)

References 34 publications

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“…Striking spectroscopic and structural differences between the two unoxidized complexes support this hypothesis. Indeed, the three infrared absorption frequencies of the carbonyl ligands appear at higher wave numbers for [Ru(P2)(CO) 3 ] than for [Fe(P2)(CO) 3 ], 12 as follows: n CO (cm…”

Section: Discussionmentioning

confidence: 99%

“…Cyclic voltammetry studies of P2, and of some of its transition metal complexes (Fe, W, Re, Mo) 12 have already been reported. They showed that coordinating the two phosphine groups of P2 drastically increases the oxidation potential of the TTF system.…”

Section: Cyclic Voltammetrymentioning

confidence: 97%

“…Indeed, much larger folding angles, up to about 251, along PÁ Á ÁP or SÁ Á ÁS hinges were observed for different P2 complexes. 11,12,34 An ORTEP representation of the complex is shown in Fig. 1. …”

Section: Structure Of [Ru(p2)(co) 3 ]mentioning

confidence: 99%

“…Finally, a comparison between the crystal structures of the neutral Ru and Fe complexes explains, in part, the differences observed in their oxidation processes. P2 (300 mg, 0.50 mmol) and Ru 3 (CO) 12 (106 mg, 0.17 mmol) were weighed in the glove-box in a Schlenk tube, then toluene (15 ml) was added. The mixture was heated for a period of 3 h, at 80 1C, under magnetic stirring.…”

Section: Introductionmentioning

confidence: 99%

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Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Gouverd

Biaso

Cataldo

et al. 2005

Phys. Chem. Chem. Phys.

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The radical cation of the redox active ligand 3,4-dimethyl-3 0 ,4 0 -bis-(diphenylphosphino)-tetrathiafulvalene (P2) has been chemically and electrochemically generated and studied by EPR spectroscopy. Consistent with DFT calculations, the observed hyperfine structure (septet due to the two methyl groups) indicates a strong delocalization of the unpaired electron on the central S 2 CQCS 2 part of the tetrathiafulvalene (TTF) moiety and zero spin densities on the phosphine groups. In contrast with the ruthenium(0) carbonyl complexes of P2 whose one-electron oxidation directly leads to decomplexation and produces P2 1 , one-electron oxidation of [Fe(P2)(CO) 3 ] gives rise to the metal-centered oxidation species [Fe (I) (P2)(CO) 3 ], characterized by a coupling with two 31 P nuclei and a rather large g-anisotropy. The stability of this complex is however modest and, after some minutes, the species resulting from the scission of a P-Fe bond is detected. Moreover, in presence of free ligand, [Fe (I) (P2)(CO) 3 ] reacts to give the complex [Fe (I) (P2) 2 (CO)] containing two TTF fragments. The two-electron oxidation of [Fe(P2)(CO) 3 ] leads to decomplexation and to the P2 1 spectrum. Besides EPR spectroscopy, cyclic voltammetry as well as FTIR spectroelectrochemistry are used in order to explain the behaviour of [Fe(P2)(CO) 3 ] upon oxidation. This behaviour notably differs from that of the Ru(0) counterpart. This difference is tentatively rationalized on the basis of structural arguments.

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Section: Discussionmentioning

confidence: 99%

Section: Cyclic Voltammetrymentioning

confidence: 97%

Section: Structure Of [Ru(p2)(co) 3 ]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Gouverd

Biaso

Cataldo

et al. 2005

Phys. Chem. Chem. Phys.

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“…In order to address this challenge, considerable effort has been devoted in associating the TTF moiety with an inorganic component and various organic mono-or polydentate ligands, and their corresponding electroactive metal complexes have therefore been reported [6]. For example, metal complexes of phosphines [7][8][9][10][11][12], dithiolates [13], acetylacetonates [14], pyridines [15][16][17], bipyridines [18,19] and more recently of Schiff bases [20][21][22] have been synthesized. Pyridine based Schiff bases ligands such as 2,6-bis(imino)pyridyl, with chelating abilities, form stable complexes, with various transition metals, which have been extensively used as catalysts for olefin polymerization [23,24].…”

Section: Open Accessmentioning

confidence: 99%

Electroactive Bisiminopyridine Ligands: Synthesis and Complexation Studies

et al. 2012

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Abstract:The condensation reaction of (4-(6,7-dimethyldithio-tetrathiafulvalene)-aniline) with 2,6-diformylpyridine afforded an electroactive Schiff base (N,N,N) pincer (3). This pincer was reacted with Zn(II) cation to yield the corresponding Zinc chloride complex (4). The crystal structure of the newly prepared electroactive zinc complex reveals that the tetrathiafulvalene (TTF) is neutral and the zinc cation is pentacoordinated. The two chlorines are involved in a set of hydrogen bonds giving rise to a 2D supramolecular grid arrangement. The electronic absorption properties and the electrochemical behavior have been elucidated. These two compounds are promising for the construction of crystalline radical cation salts.

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Redox Multifunctionality in a Series of Pt^II Dithiolene Complexes of a Tetrathiafulvalene‐Based Diphosphine Ligand

Lee¹,

Shin²,

Noh³

et al. 2009

Chemistry An Asian Journal

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The redox-active and chelating diphosphine, 3,4-dimethyl-3',4'-bis(diphenylphosphino)-tetrathiafulvalene, denoted as P2, is engaged in a series of platinum complexes, [(P2)Pt(dithiolene)], with different dithiolate ligands, such as 1,2-benzenedithiolate (bdt), 1,3-dithiole-2-thione-4,5-dithiolate (dmit), and 5,6-dihydro-1,4-dithiin-2,3-dithiolate (dddt). The complexes are structurally characterized by X-ray diffraction, together with a model compound derived from bis(diphenylphosphino)ethane, namely, [(dppe)Pt(dddt)]. Four successive reversible electron-transfer processes are found for the [(P2)Pt(dddt)] complex, associated with the two covalently linked but electronically uncoupled electrophores, that is, the TTF core and the platinum dithiolene moiety. The assignments of the different redox processes to either one or the other electrophore is made thanks to the electrochemical properties of the model compound [(dppe)Pt(dddt)] lacking the TTF redox core, and with the help of theoretical calculations (DFT) to understand the nature and energy of the frontier orbitals of the [(P2)Pt(dithiolene)] complexes in their different oxidation states. The first oxidation of the highly electron-rich [(P2)Pt(dddt)] complex can be unambiguously assigned to the redox process affecting the Pt(dddt) moiety rather than the TTF core, a rare example in the coordination chemistry of tetrathiafulvalenes acting as ligands.

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Structural and electrochemical study of metal carbonyl complexes with chelating bis- and tetrakis(diphenylphosphino)tetrathiafulvalenes

Cited by 62 publications

References 34 publications

Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Electroactive Bisiminopyridine Ligands: Synthesis and Complexation Studies

Redox Multifunctionality in a Series of Pt^II Dithiolene Complexes of a Tetrathiafulvalene‐Based Diphosphine Ligand

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Structural and electrochemical study of metal carbonyl complexes with chelating bis- and tetrakis(diphenylphosphino)tetrathiafulvalenes

Cited by 62 publications

References 34 publications

Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Tetrathiafulvalene–phosphine-based iron and ruthenium carbonyl complexes: Electrochemical and EPR studies

Electroactive Bisiminopyridine Ligands: Synthesis and Complexation Studies

Redox Multifunctionality in a Series of PtII Dithiolene Complexes of a Tetrathiafulvalene‐Based Diphosphine Ligand

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Redox Multifunctionality in a Series of Pt^II Dithiolene Complexes of a Tetrathiafulvalene‐Based Diphosphine Ligand