Rinaldo Poli

Université de Toulouse

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ÉM

Éric Manoury

Institut National Polytechnique de Toulouse

190

Jean‐Claude Daran

Laboratoire de Chimie de Coordination

153

J.‐C. Daran

Université Toulouse III - Paul Sabatier

Agnès Labande

Laboratoire de Chimie de Coordination

Jean‐Claude Daran

Centre National de la Recherche Scientifique

ÉD

Éric Deydier

Université Toulouse III - Paul Sabatier

Christophe Fliedel

Laboratoire de Chimie de Coordination

James C. Fettinger

University of California, Davis

Natalia V. Belkova

A. N. Nesmeyanov Institute of Organoelement Compounds

Kevin M. Smith

University of Michigan–Ann Arbor

Cooperative Institutions

Centre National de la Recherche Scientifique

243

Laboratoire de Chimie de Coordination

142

Université Toulouse III - Paul Sabatier

132

Institut National Polytechnique de Toulouse

115

Université de Toulouse

114

Institut de Chimie

A. N. Nesmeyanov Institute of Organoelement Compounds

Université de Bourgogne

Université de Montpellier

University of Maryland, College Park

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Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten

Organometallics (2000)

Rinaldo Poli Kevin M. Smith

The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes: C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds proceeds via a direct, metal-assisted 1,2 addition across the MCH2 bond without a distinct carbene−hydride intermediate. The relative stability order of the products can be rationalized in part through metal−ligand π-bonding considerations. The relative orbital energies, which are consistently lower for Mo than for W, can be used to rationalize various reactivity differences observed experimentally for the CpM(NO)(alkyl)2 species, including the selective coordination of small molecules. The absence of sufficient steric bulk in the model complexes likely contributes to the overestimation of the calculated activation energies and the discrepancy between some of the calculated and experimental structural parameters.

Reactivity

Cyclopentadienyl complex

Migratory insertion

Oxidative addition

Exothermic reaction

10.1021/om000088p

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Citations (17)

Solvent‐Free Epoxidation of Olefins Catalyzed by “[MoO₂(SAP)]”: A New Mode of tert‐Butylhydroperoxide Activation

ChemCatChem (2012)

Julien Morlot Nicolas Uyttebroeck Dominique Agustin Rinaldo Poli

Abstract The mononuclear molybdenum complexes [MoO 2 (acac) 2 ] ( 1 , acac=acetylacetonate), [MoO 2 (SAP)(MeOH)] ( 2 ), and dinuclear oxomolybdic complexes [MoO 2 L] 2 [L=salicylideneaminophenolato (SAP, 5 ), salicylideneaminoethanolato (SAE, 6 ), salicylideneaminomethylpropanolato (SAMP, 7 )] have been investigated as (pre)catalysts for the epoxidation of olefins under solvent‐free conditions, using tert ‐butylhydroperoxide (TBHP, 70 % in water) as an oxidant. Complexes 6 and 7 , although active, are limited by ligand hydrolysis during the catalytic process, whereas complexes 2 and 5 are not altered under catalytic conditions and yield essentially the same selectivity and activity, which is not suppressed by excess MeOH. Although these catalysts are less active than 1 , their selectivity is higher (97–98 %). DFT calculations are consistent with the active form of the catalyst being the 5‐coordinate “[MoO 2 (SAP)]”. The oxidant is activated by forming a weak adduct stabilized by a very loose Mo⋅⋅⋅O interaction and a hydrogen bond, predisposing it to the oxygen transfer to external olefin by a mechanism closely related to Bartlett’s epoxidation with peroxyacids.

10.1002/cctc.201200068

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Citations (79)

Synthesis of novel poly(N-vinyl amide)s containing copolymers by cobalt-mediated radical polymerization

Anthony Kermagoret Marie Hurtgen Ji Liu Nicolas Willet Raphaël Riva

Amide

Catalytic chain transfer

Source

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CCDC 256118: Experimental Crystal Structure Determination

The Cambridge Structural Database (2005)

A.M. Martins Carlos C. Romão Ana Margarida Abrantes M.C. Azevedo Jinlan Cui

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

10.5517/cc8lhw6

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Citations (0)

Anionic Halomolybdate(III) Chemistry. Tetrahydrofuran Loss from [MoX₃Y(THF)₂]^-(X, Y = Cl, Br, I), Preparation and Properties of [Mo₃X₁₂]³^-(X = Br, I), and Crystal Structure of the Edge-Sharing Trioctahedral [PPh₄]₃[Mo₃I₁₂]

Inorganic Chemistry (1996)

James C. Fettinger John C. Gordon Sundeep P. Mattamana Charles J. O’Connor Rinaldo Poli

By interaction of MoX(3)(THF)(3) with [Cat]X in THF, the salts [Cat][MoX(4)(THF)(2)] have been synthesized [X = I, Cat = PPh(4), NBu(4), NPr(4), (Ph(3)P)(2)N; X = Br, Cat = NBu(4), PPh(4) (Ph(3)P)(2)N]. Mixed-halide species [MoX(3)Y(THF)(2)](-) (X, Y = Cl, Br, I) have also been generated in solution and investigated by (1)H-NMR. When the tetraiodo, tetrabromo, and mixed bromoiodo salts are dissolved in CH(2)Cl(2), clean loss of all coordinated THF is observed by (1)H-NMR. On the other hand, [MoCl(4)(THF)(2)](-) loses only 1.5 THF/Mo. The salts [Cat](3)[Mo(3)X(12)] (X = Br, I) have been isolated from [Cat][MoX(4)(THF)(2)] or by running the reaction between MoX(3)(THF)(3) and [Cat]X directly in CH(2)Cl(2). The crystal structure of [PPh(4)](3)[Mo(3)I(12)] exhibits a linear face-sharing trioctahedron for the trianion: triclinic, space group P&onemacr;; a = 11.385(2), b = 12.697(3), c = 16.849(2) Å; alpha = 76.65(2), beta = 71.967(12), gamma = 84.56(2) degrees; Z = 1; 431 parameters and 3957 data with I > 2sigma(I). The metal-metal distance is 3.258(2) Å. Structural and magnetic data are consistent with the presence of a metal-metal sigma bond order of (1)/(2) and with the remaining 7 electrons being located in 7 substantially nonbonding orbitals. The ground state of the molecule is predicted to be subject to a Jahn-Teller distortion, which is experimentally apparent from the nature of the thermal ellipsoid of the central Mo atom. The [Mo(3)X(12)](3)(-) ions reacts with phosphines (PMe(3), dppe) to form products of lower nuclearity by rupture of the bridging Mo-X bonds.

Triclinic crystal system

Tetrahydrofuran

10.1021/ic9607301

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Citations (16)

CCDC 830503: Experimental Crystal Structure Determination

The Cambridge Structural Database (2011)

Yohan Champouret K. Cory MacLeod U. Baisch Brian O. Patrick K.M. Smith

10.5517/ccww6fc

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Citations (0)

CCDC 814629: Experimental Crystal Structure Determination

The Cambridge Structural Database (2011)

Y. Champoure K. Cory MacLeod Kevin M. Smith Brian O. Patrick Rinaldo Poli

10.5517/ccwbpc7

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Solvent Control in the Protonation of [Cp*Mo(dppe)H₃] by CF₃COOH

European Journal of Inorganic Chemistry (2007)

Pavel A. Dub Miguel Baya Jennifer Houghton Natalia V. Belkova Jean‐Claude Daran

Abstract The outcome of the reaction between [Cp*Mo(dppe)H 3 ] [dppe = 1,2‐bis(diphenylphosphanyl)ethane] and trifluoroacetic acid (TFA) is highly dependent on the solvent and the TFA/Mo ratio. The dihydride compound [Cp*Mo(dppe)H 2 (O 2 CCF 3 )] is obtained selectively when the reaction is carried out in aromatic hydrocarbons (benzene, toluene) when using less than one equivalent of TFA. The dihydride is also the end product when THF or MeCN are used as solvent, independent of the TFA/Mo ratio. In benzene/toluene the use of excess acid has a profound effect, resulting in the formation of the tetrahydrido complex [Cp*Mo(dppe)H 4 ] + , which did not further evolve into the dihydrido product. Monitoring of the reaction by NMR and IR spectroscopy under different conditions (solvent, temperature, TFA/Mo ratio) reveals the rapid establishment of an equilibrium between the dihydrogen‐bonded adduct, [Cp*Mo(dppe)H 3 ] ··· HO 2 CCF 3 , the ion‐paired proton‐transfer product, [Cp*Mo(dppe)H 4 ] + ··· – O 2 CCF 3 , and the separated ions, followed by a slower irreversible transformation to the final dihydride product with H 2 evolution. The activation parameters of the H 2 evolution and M–OR product formation were determined. Excess TFA in low‐polarity solvents stabilizes the separated charged species by forming the homoconjugate anion [CF 3 COO(CF 3 COOH) n ] – . The effect of the solvent on the course of the reaction can be interpreted in terms of the different polarity, H‐bonding ability, and coordinating power of the various solvent molecules.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Trifluoroacetic acid

10.1002/ejic.200700021

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Citations (26)

Key role of metal-coordination in cobalt mediated radical polymerization

Antoine Debuigne Rinaldo Poli Christine Jérôme Robert Jérôme Christophe Detrembleur

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One-Pot RAFT Synthesis of Triphenylphosphine-Functionalized Amphiphilic Core-Shell Polymers and Application as Catalytic Nanoreactors in Aqueous Biphasic Hydroformylation

ACS symposium series (2015)

Rinaldo Poli Si Chen Xuewei Zhang Andrés F. Cardozo Muriel Lansalot

Controlled radical polymerization has recently been used to develop polymers engineered for applications as catalytic nanoreactors. In this contribution, we present the joint development, in our laboratories, of core-cross-linked micelles (CCM) for application under aqueous biphasic conditions through the micellar approach, using triphenylphosphine (TPP) as polymer-anchored ligand and rhodium as catalytic metal for the hydroformylation of 1-octene as a model α-olefin. The polymers were synthesized by a one-pot convergent approach using RAFT as controlling method in water, making use of the polymerization-induced self-assembly (PISA) principle. The article will also show the polymer properties in terms of size, polydispersity, swelling, metal coordination and exchange, and interpenetration. It will also illustrate our initial catalytic studies with focus on the effect of the polymer architecture (ligand nature, ligand density, core size, nature of cross-linking) and of the stirring rate on the catalytic performance (turnover frequency) and catalyst leaching.

Nanoreactor

Dispersity

Raft

10.1021/bk-2015-1188.ch014

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Citations (12)