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1. 1,3-Diethynyl-5-(X)-benzene-Bridged [Cp*(dppe)Fe]n+ Units: Effect of Substituents on the Metal-Metal Interactions

Author

Joseph Lepont, Jean-René Hamon, Claude Lapinte, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Acetylides, 010402 general chemistry, Charge localization, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Mixed-Valence, chemistry.chemical_compound, chemistry, Polymer chemistry, Organoiron, [CHIM]Chemical Sciences, Metal metal, Benzene, Molecular structure
Abstract

International audience; The new complexes [1,3-{Cp*(dppe)Fe−C≡C-}2-5-(X)-(C6H3)] (X=CH3, [m-1 b]; X=C(O)OCH3, [m-1 c]; X=C≡C-4-C6H4-C(O)OCH3, [m-1 d]; X=C≡C-4-C6H4-NO2, [m-1 e]) were prepared by reaction of the iron chloride Cp*(dppe)FeCl (4) and the proligands 3 b-e obtained by a cross coupling reaction between the suitable aryl dibromides and trimethylsylilacethylene. After purification the complexes [m-1 b–e] were isolated in yields ranging from 14 to 37 % and characterized by elemental analysis, high-resolution, ESI-mass spectra, multinuclear NMR, cyclic voltammetry, and IR spectroscopy. The complexes [m-1 b], [m-1 d], and [m-1 e] were also characterized by XRD analyses on single crystals. The doubly oxidized complexes [m-1 b–e](PF6)2 were prepared (in ca. 64–87 % yields) by treatment of a CH2Cl2 solution of the corresponding neutral complexes [m-1 b–e] with two equiv. of [(C5H5)2Fe](PF6). The mixed-valence complexes (MV) [m-1 b–e](PF6) were obtained by comproportionation between one equiv. of [m-1 b–e] and one equiv. of [m-1 b–e](PF6)2. CV, IR and NIR data led to the conclusion that the MV [m-1 b–e](PF6) complexes are weakly coupled Class II MV derivatives and the distribution of the charge between the alkynyl iron centers and the phenyl ring might be tuned by the X-substituents in a limited extend. © 2021 Wiley-VCH GmbH.

Published
2021
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2. 1,4-Diethynylbenzene-Bridged [Cp*(dppe)Fe](n+) Units: Effect of 2,5-Ethynyl Groups on the Chemical and Electronic Properties

Author

Jean-René Hamon, Jean-François Halet, Vincent Dorcet, Samia Kahlal, Thierry Roisnel, Thomas Groizard, Rim Makhoul, Paul Hamon, Claude Lapinte, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), GENCI (Grand Equipment National de Calcul Intensif) [GENCI A0030807367], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Iron, Population, Acetylides, 010402 general chemistry, Mass spectrometry, Ring (chemistry), 01 natural sciences, Quantum chemistry, Inorganic Chemistry, Deprotonation, Mössbauer spectroscopy, Bridge-centered radicals, [CHIM]Chemical Sciences, Mixed-valence, education, Electronic properties, Electronic coupling, education.field_of_study, 5-Ethynyl Groups on the Chemical and Electronic Properties, 010405 organic chemistry, Chemistry, 0104 chemical sciences, Magnetic coupling, Crystallography, Yield (chemistry), 4-Diethynylbenzene-Bridged [Cp*(dppe)Fe]n+ Units: Effect of 2
Abstract

International audience; The bis(ironvinylidene) complex [1,4-{Cp*(dppe)Fe=C=CH}(2)-2,5-(C equivalent to CH)(2)-C6H2](PF6)(2) ([2-2H](PF6)(2)) was prepared from 1,2,4,5-tetraethynylbenzene and two equiv. of Cp*(dppe)FeCl in 87 % yield. The reaction is very selective and [2-2H](PF6)(2) is the unique organoiron species to be formed. Deprotonation of [2-2H](PF6)(2) provided the target complex 2 (66 % yield) and subsequent oxidation gave the monocationic and dicationic complexes 2(PF6) and 2(PF6)(2). The new complexes were characterized by ESI-mass spectrometry, IR, multinuclear NMR, ESR and Mossbauer spectroscopy, and XRD analyses on single crystals for [2-2H](PF6)(2) and 2(PF6)(2). The magnetic properties of 2(PF6)(2) were investigated by VT H-1 NMR. The data were analyzed with the support of quantum chemistry calculations. The terminal ethynyl groups on the aromatic ring of the bridge modify the population of the bridge-oxidized state, weaken the electronic communication (H-ab approximate to 601 cm(-1)) and strengthen magnetic coupling interactions (J = -530 cm(-1)) compared to the unsubstituted species (H-ab = 1700 cm(-1) and J = -340 cm(-1), respectively).

Published
2020
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3. A Tetrairon Dication Featuring Tetraethynylbenzene Bridging Ligand: a Molecular Prototype of Quantum-Dot Cellular Automata

Author

Claude Lapinte, Thierry Roisnel, Paul Hamon, Jean-René Hamon, Rim Makhoul, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Quantum dot cellular automaton, Disproportionation, Bridging ligand, General Chemistry, organoiron, 010402 general chemistry, tetraethynylbenzene bridge, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, Dication, Crystallography, Yield (chemistry), QCA (quantum cellular automata), Molecule, mixed-valence, [CHIM]Chemical Sciences, charge container, Single crystal
Abstract

International audience; The unprecedented tetrairon dication [{Cp*(dppe)FeC≡C-} -μ-(1,2,4,5-C H )](PF ) (1) was obtained through a sequence of three reactions from 1,2,4,5-tetraethynylbenzene, Cp*(dppe)FeCl (Cp*=C Me , dppe=1,2-bis(diphenylphosphino)-ethane), KOtBu, and ferrocenium hexafluorophosphate. The cyclic voltammogram of the target molecule, isolated in 77 % yield, exhibits four well separated and reversible redox events showing that 1 is thermodynamically stable with respect to disproportionation (Kc>10 ). The tetranuclear dication 1 was characterized by XRD on single crystal, IR and NMR spectroscopies and Mössbauer spectrometry. The experimental data show that 1 behaves as a class II mixed-valence complex with the positive charges preferentially disposed on antipodal positions. This new molecule can be regarded as a potential molecular prototype of quantum dot cellular automata.

Published
2020
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4. Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers

Author

Diego Venegas-Yazigi, Verónica Paredes-García, Evgenia Spodine, Francisco Rubio, Christophe Calers, Nathalie Audebrand, Carlos Cruz, Universidad Andrés Bello [Santiago] (UNAB), Centro para el Desarrollo de la Nanociencia y Nanotecnología (CEDENNA), Universidad de Santiago de Chile [Santiago] (USACH), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Chile = University of Chile [Santiago] (UCHILE), FONDECYT Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT [1170887], Proyecto Anillo CONICYT ACT [1404, 1027, ECOS/CONICYTC15E02], CEDENNA, Financiamiento Basal [FB0807], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Universidad de Chile

Subjects
chemistry.chemical_classification, Materials science, Valence (chemistry), 010405 organic chemistry, Rational design, Magnetism, chemistry.chemical_element, Gadolinium, General Chemistry, Polymer, Coordination Polymers, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Copper, 0104 chemical sciences, 3d-4f, Mixed-Valence, Crystallography, chemistry, [CHIM]Chemical Sciences, General Materials Science
Abstract

International audience; I 2 (4,4'-bipy)]·4.5H 2 O 2 obtained under solvothermal synthesis using 1H-imidazole-4,5-dicarboxylic acid (H 3 IDC) as principal N,O-bifunctional organic linker. In both compounds, the stabilization of the Cu I cations is achieved only by the coordination of N-atoms belonging to the organic ligands. While, 1 presents a 2D honeycomb network obtained by the coordination of single organic linker (IDC 3-), 2 contains three different organic ligands (IDC 3-, C 2 O 4 2-and 4,4'-bipy), which allow the construction of a 3D network. From a magnetic point of view, 1 and 2 behave as simple paramagnets at high temperature, presenting ferromagnetic interactions below 50 K, a positive magnetic coupling constant of J = 0.60 cm-1 and J = 0.22 cm-1 was obtained for 1 and 2 respectively. To the best our knowledge 1 and 2 correspond to the second and third reported examples containing a Cu I /Cu II mixed valence system assembled with Gd III cations, thus enriching the chemistry involved in the 3d-4f metal-organic materials.

Published
2019
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5. Charge delocalization vs localization in carbon-rich iron mixed-valence complexes: A subtle interplay between the carbon spacer and the (dppe)Cp*Fe organometallic electrophore

Author

Claude Lapinte, Jean-François Halet, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Iron, Inorganic chemistry, Conjugated system, 010402 general chemistry, Electrochemistry, 01 natural sciences, law.invention, Inorganic Chemistry, Delocalized electron, Carbon-rich systems, law, Mössbauer spectroscopy, Materials Chemistry, Mixed-valence, Magnetic exchange, Physical and Theoretical Chemistry, Electron paramagnetic resonance, Valence (chemistry), 010405 organic chemistry, Chemistry, Inductive coupling, Potential energy, 0104 chemical sciences, Organometallic, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Metal-metal coupling
Abstract

International audience; In this review, the electronic and structural properties of different organometallic wires containing the (dppe)Cp*Fe organometallic electrophore are thoroughly discussed. Results obtained from X-ray crystallography, electrochemistry, IR, NIR, NMR, EPR and 57Fe Mössbauer spectroscopy measurements, as well as theoretical calculations serve to illustrate how electron-transfer in the mono-oxidized mixed-valence species and magnetic coupling in the di-oxidized species can be mediated by different conjugated and non-conjugated carbon linkers. Electron-transfer reactions in the former are generally described by two-state potential energy curves of the Marcus-Hush type. We will see that this model does not always apply, emphasizing the non-innocent role of the carbon-rich bridge in some cases.

Published
2013
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6. High-dimensional mixed-valence copper cyanide complexes: Syntheses, structural characterizations and magnetism

Author

Jean Sala-Pala, Franck Thétiot, Samia Benmansour, Fatima Setifi, Carlos J. Gómez-García, Enrique Colacio, Smail Triki, 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), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), Departamento de Química Inorgánica, and Universidad de Granada (UGR)

Subjects
Denticity, Magnetism, Inorganic chemistry, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Coordination modes, Ion, Inorganic Chemistry, Paramagnetism, Magnetic properties, Materials Chemistry, Mixed-valence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Valence (chemistry), Bridging ligands, 010405 organic chemistry, Ligand, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Copper, 0104 chemical sciences, Crystallography, Copper cyanides, chemistry, CN-group
Abstract

International audience; Reactions of CuCl 2 with different CN complexes in presence of a neutral ancillary ligand lead to two novel mixed-valence Cu complexes [Cu II (bpy)Cu I (CN) 3 ] n , 1 (bpy=2,2′-bipyridine) and {[Cu II (tn) 2 ][Cu I 4 (CN) 6 ]} n 2 (tn=1,3-diaminopropane). For compound 1, the asymmetric unit involves two Cu ions Cu1 and Cu2 (Cu I and Cu II centres, respectively) which strongly differ in their environments. The Cu1 ion presents a CuC 4 pseudo-tetrahedral geometry, while the Cu2 ion presents a CuN 5 slightly distorted square-pyramidal geometry. The extended structure of 1 is generated by three cyano ligands which differ in their coordination modes. One CN group has a μ 3 coordination mode and bridges two Cu I and one Cu II ion, while the two other CN groups act as μ 2 bridges leading to a sophisticated 3-D structure. As for 1, the asymmetric unit of 2 involves three crystallographically different Cu ions (Cu1A and Cu1B, presumably Cu I centres, and Cu2 presumably Cu II centres). The Cu2 ion presents centrosymmetric CuN 4 coordination environments involving four nitrogen atoms from two bidentate tn ligands; while the Cu1A and Cu1B ions are three coordinated to cyano groups. The structure can be described as formed by 18-membered “[Cu I (CN)] 6 ” planar metallocycles that are connected to their six neighbors to generate 2-D sheets; these sheets stack forming infinite hexagonal channels in which the [Cu(tn) 2 ] 2+ units are located. Magnetic measurements show an unexpected weak ferromagnetic coupling (θ=0.239(1)K) of the Cu II ions through the long and “a priori diamagnetic” –NC–Cu I –CN– bridges in compound 1 and an essentially paramagnetic behavior in compound 2.

Published
2009
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7. On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)} 2 (μ-dicyd)][PF 6 ] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione

Author

Jacques Bonvoisin, Jean-Pierre Launay, Mohamed Hliwa, Joël Jaud, Muriel Fabre, Groupe NanoSciences (CEMES-GNS), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Université Hassan II [Casablanca] (UH2MC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Non innocent bridging ligand, Ruthenium complexes, Electron-transfer, chemistry.chemical_element, DFT calculation, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, law.invention, Inorganic Chemistry, X-ray, chemistry.chemical_compound, Electron transfer, dicyanamidobenzene, law, Mixed-valence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, structure, Physical and Theoretical Chemistry, Electron paramagnetic resonance, Spectroelectrochemistry, 010405 organic chemistry, Electrochemical, Magnetic susceptibility, 3. Good health, 0104 chemical sciences, Ruthenium, Crystallography, chemistry, Intramolecular force, properties, Terpyridine, Cyclic voltammetry, Hole-transfer, EPR spectroscopy
Abstract

The dicyanamidobenzene-bridge diruthenium complex [{Ru(tpy)(thd)}(2)(mu-dicyd)][PF(6)] ([3][PF(6)]) (dicyd = 1,4-dicyanamidobenzene, tpy = 2,2':6',2' '-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and its mononuclear counterpart [Ru(tpy)(thd)(Ipcyd)] (2) [Ipcyd = 4-iodophenylcyanamide anion (Ipcyd(-))] were synthesized and fully characterized. Cyclic voltammetry of 3 showed the presence of four reversible one-electron redox couples. UV-vis-NIR spectroelectrochemistry and EPR spectroscopy of the electrogenerated paramagnetic intermediates were used to ascertain the oxidation-state distribution. The stable starting dinuclear complex 3(+) is found to be a ligand-centered anion radical as shown by EPR spectroscopy, magnetic susceptibility measurements, and DFT calculations. Oxidation of 3(+) to 3(2+) led to an EPR silent system due to substantial intramolecular antiferromagnetic interaction of the electron spins carried by the low spin ruthenium(III) atom and the bridging anion radical dicyanamido (dicyd(*)(-)), an observation which was supported by UV-vis-NIR, X-ray structure, and DFT calculations. Complex 3(3+) presented an EPR spectra consistent with a total effective spin S = (1)/(2) issued from an antiferromagnetic interaction of electron spins carried by two low spin ruthenium(III) atoms and the bridging anion radical dicyd(*)(-) in accordance with UV-vis-NIR. This study shows that the dicyanamidobenzene bridging ligand has indubitably a noninnocent behavior.

Published
2006
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8. Mono- and dinuclear oxomolybdenum complexes containing the [TCNQ].- radical anion. Crystal structure of [MoO(Et2NCS2)3]TCNQ.THF, an example of an almost perfectly eclipsed [(TCNQ)2]2- dimer

Author

Decoster, M., Conan, Françoise, Le Mest, Yves, Sala Pala, J., Leblanc, A., Molinie, P., Faulques, E., Toupet, Ludovic, University of Ottawa [Ottawa], 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), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and RENARD, NICOLAS

Subjects
Molybdenum, TCNQ, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Dithiocarbamato, Mixed-valence, Oxocompounds
Abstract

International audience; The reactions between TCNQ and the molybdenum (V) dinuclear complexes [Mo2O3(dtc)4] 1a-c (dtc = Et2NCS2 for 1a; Me2NCS2 for 1b; Pr2NCS2 for 1c) afford the molybdenum (VI) mononuclear complexes [MoO(dtc)3]TCNQ 2a-c. 2a can also be obtained from the molybdenum (IV) complex [MoO(dtc)2] 4a by reaction with Et2NC(S)SSC(S)NEt2 and TCNQ or from the molybdenum (VI) complex [MoO(dtc)3]BF4 3a by treatment with LiTCNQ. 2a reacts with TCNQ to give the TCNQ complex salt [MoO(dtc)3](TCNQ)2 5a and with triphenylphosphine to yield the mixed-oxidation state dinuclear complex [Mo2O(dtc)6](TCNQ) 7a; the reaction of 7a with TCNQ gives back 2a. The electrochemical and magnetic properties of these complexes are presented and discussed. The crystal structure of 2a has been determined by X-ray diffraction methods. Least-squares refinement of the structure based on 3489 unique data led to final discrepancy indices of R = 0.025 and Rw = 0.024. The crystal structure consists of [(TCNQ)2]2- anions with an unusual and quasi-perfect eclipsed geometry associated with [MoO(dtc)3]+ cations having a distorted pentagonal bipyramid geometry. © CNRS-Gauthier-Villars.

Published
1997

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