A5004284214- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organometallic Complex Synthesis and Catalysis
- Asymmetric Hydrogenation and Catalysis
- Crystallography and molecular interactions
- Metal complexes synthesis and properties
- Magnetism in coordination complexes
- Hydrogen Storage and Materials
- Boron Compounds in Chemistry
- Organoboron and organosilicon chemistry
- Catalytic Cross-Coupling Reactions
- Advanced Chemical Physics Studies
- Carbon dioxide utilization in catalysis
- Ammonia Synthesis and Nitrogen Reduction
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Inorganic Fluorides and Related Compounds
- Metal-Organic Frameworks: Synthesis and Applications
- Radioactive element chemistry and processing
- Fluorine in Organic Chemistry
- Synthetic Organic Chemistry Methods
- Photorefractive and Nonlinear Optics
- Synthesis and characterization of novel inorganic/organometallic compounds
- Photonic and Optical Devices
- Chemical Reactions and Isotopes
- Advanced Fiber Laser Technologies
A. N. Nesmeyanov Institute of Organoelement Compounds
2016-2025
A.E. Arbuzov Institute of Organic and Physical Chemistry
2023
Russian Academy of Sciences
2008-2021
Institute of Bioorganic Chemistry
2019-2021
Universitat Autònoma de Barcelona
2006-2010
Université de Toulouse
2009
Institut National Polytechnique de Toulouse
2009
Université Toulouse III - Paul Sabatier
2009
Centre National de la Recherche Scientifique
2009
Institut Universitaire de France
2009
Deprotonation of the MnI NHC-phosphine complex fac-[MnBr(CO)3 (κ2 P,C-Ph2 PCH2 NHC)] (2) under a H2 atmosphere readily gives hydride fac-[MnH(CO)3 (3) via intermediacy highly reactive 18-e NHC-phosphinomethanide fac-[Mn(CO)3 (κ3 P,C,C-Ph2 PCHNHC)] (6 a). DFT calculations revealed that preferred reaction mechanism involves unsaturated 16-e mangana-substituted phosphonium ylide P=CHNHC)] b) as key intermediate able to activate non-classical mode metal-ligand cooperation implying formal λ5...
Abstract Systematic modification of the chelating NHC‐phosphine ligand (NHC = N ‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac ‐[(Ph 2 PCH NHC)Mn(CO) 3 Br] has been performed and catalytic activity resulting complexes was evaluated using acetophenone as a benchmark substrate. While variation phosphine NHC moieties led to inferior results than for parent system, incorporation phenyl substituent into methylene bridge improved performance by ca . times...
The ring-opening metathesis polymerization (ROMP) of functional norbornenes, i.e., exo,endo-5-norbornene-2-carbonitrile (3), methyl (exo,endo-5-norbornene-2-carboxylate) (4), norborn-5-ene-2-yl acetate (5), 2-propyl exo,endo-5-norbornene-2-carboxylate (6), norborn-5-ene-2-carboxylic acid (7), exo,endo-5-norbornene-2-methanol (8), exo,endo-5-norbornene-2-ylmethyl bromide (9), exo,endo-5-norbornene-2-ylmethylamine (10), exo,endo-5-norbornene-2-triethoxysilane (11), dimethyl...
The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO<sub>1.5</sub>)<sub>20</sub>(FeO<sub>1.5</sub>)<sub>6</sub>(NaO<sub>0.5</sub>)<sub>8</sub>(<italic>n</italic>-BuOH)<sub>9.6</sub>(C<sub>7</sub>H<sub>8</sub>)] (<bold>I</bold>) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses DFT calculation.
The series of bimetallic complexes (tBuPXCYP)Pd(μ-OC)M(CO)2L (X, Y = CH2, O; M W, Mo; L Cp, Tp) catalyzes formic acid decomposition into H2/CO2 in fairly mild conditions (25–50 °C, toluene) without any organic base additives. catalytic activity increases with CH2-substitution the O-bridges (PXCYP)-frame as well proton-donating ability Mo/W hydride. best result was obtained (tBuPCP)Pd(μ-OC)Mo(CO)2Cp (3), which gives complete conversion at 2 mol % loading 30 min 50 °C (TOF 100 h–1). During...
Abstract Despite the significance of H 2 O -metal adducts in catalysis, materials science and biotechnology, nature interactions between metal cations remains elusive debatable. This is primarily due to extremely weak coordinating ability , which poses challenges characterizing understanding specific these interactions. Herein, we present an approach obtain –metal complexes that employs neat as both solvent ligand. SnCl 4 effectively binds forming a (H ) complex, confirmed by 119 Sn 17 NMR...
The grafting of a -(CH2)2PR3+ moiety on an NHC ligand backbone in the Mn(I) complex [Cp(CO)2Mn(IMes)] followed by double deprotonation opens route to bidentate ligands with extreme electron-donating character. Such remarkable electronic properties can even allow intramolecular sp2 C-H functionalization typically inert square-planar Rh(I) dicarbonyl complexes.
Half‐sandwich 18e rhodium iminophosphonamide complexes [Сp*RhCl(NPN)] with NPN = Ph2P(N‐p‐Tol)2 (1a), Ph2P(N‐p‐Tol)(NMe) (1b) and 16e cationic [Сp*Rh(NPN)](PF6) (2a+PF6‐) were found to catalyze transfer hydrogenation of carbonylic substrates (acyclic cyclic alkyl ketones, aromatic ketones aldehydes) the activity strongly enhanced by presence chloride ligand. Kinetic studies including KIE activation parameters measurements carried out for two model (acetophenone cyclohexanone) as well...
Reaction of the acidic tungsten(II) hydride 2 with nickel(II) pincer complex 1 in either THF or toluene after an initial dihydrogen bonding (DHB) interaction led to formation Ni–W bimetallic species 3 (see picture). The first example DHB between two metal hydrides opposite polarity was analyzed by NMR and IR spectroscopy, X-ray crystallography, DFT calculations. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...
The IrIII hydride (tBuPCN)IrHCl (1) containing the tridendate unsymmetrical pincer ligand tBuPCN– {tBuPCN(H) = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole} has been exploited as ammonia borane (NH3BH3, AB) and amine boranes dehydrogenation catalyst in THF solution at ambient temperature. 1 releases one H2 equivalent per AB equivalent, with concomitant cyclic poly(aminoboranes) formation [B-(cyclotriborazanyl)-amine-borane (BCTB) cyclotriborazane (CTB)] final "spent fuel". found...
The first example of trinuclear copper(I) and silver(I) pyrazolates adducts with a tertiary diphosphine (Ph2PCH2PPh2) retaining trimeric [MPz]3 core is reported. Despite rather strong M-P bonding, the complexes are able to undergo dissociation one bond leading "merry-go-round" movement P atoms over M3 triangle. copper complex displays emission from 1MLCT 3MLCT states. triplet singlet states separated by relatively small energy gap (1080 cm-1) that triggers thermally activated delayed...
Ligand–metal cooperation: A new ligand–metal cooperating catalyst for the hydroformylation of olefins is described (see scheme). The mechanism H2 activation and CH bond formation involves an intramolecular cooperation between structurally remote functionality metal center proceeds without change oxidation state metal. As a service to our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized online delivery,...
Bifunctional dibenzobarrelene-based PC(sp3)P pincer iridium complex 1 is known as an efficient catalyst in acceptorless dehydrogenation of alcohols and hydrogenation/hydroformylation alkenes. In order to shed light on the mechanism hydrogen formation/activation, we performed variable-temperature IR NMR (1H, 31P) analysis intra- intermolecular interactions involving a hydride ligand hydroxymethyl cooperating group its analogues. The results spectroscopic measurements different media...
The title complex (tBuPCP)IrH(Cl) (1; tBuPCP = κ3-2,6-(CH2PtBu2)2C6H3) appeared to be moderately active in NHMe2·BH3 (DMAB) dehydrogenation, allowing the systematic spectroscopic (variable-temperature NMR and IR) investigation of reaction intermediates products, under both stoichiometric catalytic regimes, combined with DFT/M06 calculations. formation hexacoordinate (tBuPCP)IrHCl(η1-BH3·NHMe2) (3) stabilized by a NH···Cl hydrogen bond is shown experimentally at first step. This activates B–H...
Two Co(I) hydrides containing the tripodal polyphosphine ligand EP3, (κ4-EP3)Co(H) [E(CH2CH2PPh2)3; E = N (1), P (2)], have been exploited as ammonia borane (NH3BH3, AB) dehydrogenation catalysts in THF solution at T 55 °C. The reaction has analyzed experimentally through multinuclear (11B, 31P{1H}, 1H) NMR and IR spectroscopy, kinetic rate measurements, isotope effect (KIE) determination with deuterated AB isotopologues. Both complexes are active dehydrogenation, albeit different rates...
Silver(<sc>i</sc>) pyrazolate adducts with phenanthroline, neocuproine and bathocuproine exhibit phosphorescence in the solid state. Their photophysical behavior was interpreted using TD-DFT calculations.
Unprecedented cooperation between mononuclear cationic and hydride metal complexes enables highly efficient Mn-catalyzed hydrogen production from various amine-boranes at low catalyst loading.
Interaction of the copper, {[3,5-(CF3)2Pz]Cu}3, and silver, {[3,5-(CF3)2Pz]Ag}3, macrocycles [3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate] with cyclooctatetraeneiron tricarbonyl, (cot)Fe(CO)3, was investigated by IR NMR spectroscopy for first time. The formation 1:1 complexes observed at low temperatures in hexane. composition (1:1) their thermodynamic characteristics hexane dichloromethane were determined. π-electron system (cot)Fe(CO)3 proven to be sole site coordination solution...
The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on example (Ph3P)2Cu(η2-BH4) interaction with different proton donors [MeOH, CH2FCH2OH, CF3CH2OH, (CF3)2CHOH, (CF3)3CHOH, p-NO2C6H4OH, p-NO2C6H4N═NC6H4OH, p-NO2C6H4NH2] using combination experimental (IR, 190–300 K) and quantum-chemical (DFT/M06) methods. formation dihydrogen-bonded complexes as reaction step experimentally. Their structural, electronic, energetic, spectroscopic features were...
Methylsulfanyl derivatives of cobalt bis(dicarbollide), [8,8′‐(MeS) 2 ‐3,3′‐Co(1,2‐C B 9 H 10 ) ] – , [4,4′‐(MeS) and [4,7′‐(MeS) were synthesized through the reactions CoCl with [10‐MeS‐7,8‐C 11 [9‐MeS‐7,8‐C in strong alkaline aqueous media. The 4,4′‐( rac 4,7′‐( meso isomers separated by column chromatography as tetrabutylammonium salts. structures [Bu 4 N][8,8′‐(MeS) ], N][4,4′‐(MeS) N][4,7′‐(MeS) determined single‐crystal X‐ray diffraction. In solid state, rotation two dicarbollide...
Abstract Half‐sandwich manganese methylenephosphonium complexes [Cp(CO) 2 Mn(η ‐R PC(H)Ph)]BF 4 were obtained in high yield through a straightforward reaction sequence involving classical Fischer‐type complex and secondary phosphine as key starting materials. The addition of various nucleophiles (Nu) to these species took place regioselectively at the double‐bonded carbon center coordinated ligand R P + C(H)Ph produce corresponding chiral Mn(κ 1 PC(H)(Ph)Nu)], from which phosphines...