A5071911157- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organometallic Complex Synthesis and Catalysis
- Crystallography and molecular interactions
- Asymmetric Hydrogenation and Catalysis
- Carbon dioxide utilization in catalysis
- CO2 Reduction Techniques and Catalysts
- Catalytic C–H Functionalization Methods
- Magnetism in coordination complexes
- Nanocluster Synthesis and Applications
- Synthesis and Catalytic Reactions
- Synthesis and characterization of novel inorganic/organometallic compounds
- Metal complexes synthesis and properties
- Molecular Junctions and Nanostructures
- MXene and MAX Phase Materials
- Inorganic Chemistry and Materials
- Catalytic Cross-Coupling Reactions
- 2D Materials and Applications
- Advanced Chemical Physics Studies
- Organoboron and organosilicon chemistry
- Cyclopropane Reaction Mechanisms
- Oxidative Organic Chemistry Reactions
- Graphene research and applications
- Advanced Chemical Sensor Technologies
- Metal-Organic Frameworks: Synthesis and Applications
Consorzio Roma Ricerche
2025
Institute for the Chemistry of OrganoMetallic Compounds
2015-2024
National Research Council
2021
Université de Rennes
2010-2017
Centre National de la Recherche Scientifique
2010-2017
Institut des Sciences Chimiques de Rennes
2010-2017
Cornell University
2016
University of Milan
2015
Université Européenne de Bretagne
2010-2012
University of Pisa
2009-2010
A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. combination UV-vis-NIR IR spectroelectrochemical methods density functional theory (DFT) used to demonstrate that one-electron oxidation compounds [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)](HC≡CArC≡CH 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene;...
A DFT-based theoretical analysis describes the allylic amination of cyclohexene by 3,5(CF3)2phenylazide catalyzed [Ru](CO) ([Ru]= Ru(TPP), TPP = dianion tetraphenylporphyrin). The activation an azide molecule (RN3) at free ruthenium coordination site allows formation a monoimido complex [Ru](NR)(CO) with eco-friendly dismissal N2 molecule. can undergo singlet→triplet interconversion to confer diradical character RN ligand. Hence, C–H bond (C6H10) occurs through C–H···N interaction over...
We studied the chemical-physical nature of interactions involved in formation adducts two-dimensional black phosphorus (2D BP) with organoboron derivatives a conjugated fluorescent molecule (pyrene). Time-resolved fluorescence spectroscopy showed stabilization effect 2D BP on all derivatives, particular for endowed boronic functionalities. Also, stronger modulation decay oxygen was registered one compared to corresponding derivative alone. Nuclear magnetic resonance experiments suspension...
In the quest for highly active ruthenium(II) complexes homogeneous catalytic CO2 hydrogenation to formate, a small library of cationic Ru(k3-tpm) piano-stool [tpm = tris(pyrazolyl)methane], bearing different ancillary ligands, were tested under various reaction conditions, with and without addition Lewis acid co-catalyst. Under optimized conditions (80 bar, 120 °C) in presence LiOTf, TONs > 54000 obtained single batch runs complex [RuCl(k3-tpm)(PPh3)(CH3CN)]Cl (1). Mechanistic studies...
In the quest for highly active ruthenium(II) complexes homogeneous catalytic CO2 hydrogenation to formate, a small library of cationic Ru(k3-tpm) [tpm = tris(pyrazolyl)methane], bearing different ancillary ligands, were tested under various reaction conditions, with and without addition Lewis acid co-catalyst. Under optimized conditions (80 bar, 120 °C) in presence LiOTf, TONs > 54000 obtained single batch runs complex [RuCl(k3-tpm)(PPh3)(CH3CN)]Cl (1). Mechanistic studies using NMR...
This paper investigates geometric and electronic features of linear I3– I42– anions, as building blocks larger polyiodides. Most experimental structures are quasi D∞h, although one lateral linkage is occasionally elongated with I···I separations approaching those I···I–R– species, typical halogen bonding (HalB). Hirshfeld surfaces from crystal data highlight solid state effects depending on the distribution counterions around or units. Corresponding asymmetries have been mimicked density...
The oxidation of organic sulphides with aqueous hydrogen peroxide in ionic liquids (ILs) catalysed by oxodiperoxomolybdenum complexes was investigated. selective formation several sulfones achieved using the 1 : 3 ratio sulphide H2O2 [C4mim][PF6] (C4mim = 1-butyl-3-methylimidazolium) a reaction [Mo(O)(O2)2(H2O)n] complex. Conversely, sulfoxides were produced good selectivities same solvent h [Mo(O)(O2)2(Mepz)2] (Mepz methylpyrazol). use as advantageous for two reasons: (i) improved...
A combination of DFT and kinetic studies suggests a mechanism for olefin aziridination by organic azides catalysed ruthenium porphyrins.
Abstract The cost‐effective TPPH 2 /TBACl‐catalyzed (TPPH =dianion of tetraphenyl porphyrin; TBACl=tetrabutyl ammonium chloride) carbon dioxide cycloaddition to N ‐aryl aziridines was successful in synthesizing oxazolidin‐2‐ones. A catalytic tandem reaction also developed, which were initially synthesized and then reacted with without being purified. procedure occurred a very high atom economy, molecular nitrogen the only by‐product entire process. In addition, mechanism cycle investigated...
The chemical functionalization of 2D exfoliated black phosphorus (2D BP) continues to attract great interest, although a satisfactory structural characterization the functionalized material has seldom been achieved. Herein, we provide first complete BP with rare discrete Pd2 units, obtained through mild decomposition organometallic dimeric precursor [Pd(η3-C3H5)Cl]2. A multitechnique approach, including HAADF-STEM, solid-state NMR, XPS, and XAS, was used study in detail morphology palladated...
The protonation of commercially available porphyrin ligands yields a class bifunctional catalysts able to promote the synthesis N-alkyl oxazolidinones by CO
A Colour Catcher® sheet was employed as a solid support for immobilizing biologically derived porphyrin species. The resulted cheap, user-friendly and recyclable material efficient in catalyzing the CO 2 cycloaddition to three-membered rings.
The exchange-coupling constants in dinuclear 1,1-azidonickel(II) complexes and one tetranuclear complex have been analyzed by using electronic structure calculations based on density functional theory. calculated J values show a correlation with the Ni-N-Ni angle; however, available experimental data do not present between both magnitudes. Hence, new fitting procedures were carried out to obtain set of fitted for all reported complexes. These better angle close that found theoretical...
A detailed hybrid density functional theory study was carried out to clarify the mechanism of Ru-catalyzed dehydrogenation formic acid in presence octahedral complexes [Ru(κ4-NP3)Cl2] (1) and [Ru(κ3-triphos)(MeCN)3](PF6)2 (2·PF6) [NP3 = N(CH2CH2PPh2)3, triphos MeC(CH2PPh2)3]. It shown that Ru-hydrido vs Ru-formato species are pivotal bringing about efficient release H2 CO2 following either a metal-centered (inner-sphere) or ligand-centered (outer-sphere) pathway, respectively.
This paper is a comparative outline of the potential acid–base adducts formed by an unsaturated main group or transition metal species and P atoms phosphorene (P<sub>n</sub>), which derives from black phosphorus exfoliation.
The compound [Ru(CNtBu)4(Cl)2], 1, reacts with I2, yielding the halogen-bonded (XB) 1D species {[Ru(CNtBu)4(I)2]·I2}n, (2·I2)n, whose building block contains I– ligands in place of Cl– ligands, even though no suitable redox agent is present solution. Some isolated solid-state intermediates, such as {[Ru(CNtBu)4(Cl)2]·2I2}n, (1·2I2)n, and {[Ru(CNtBu)4(Cl)(I)]·3I2}n, (3·3I2)n, indicate stepwise substitution two trans-halide showing that end-on-coordinated trihalides play a key role process. In...
The reaction between Pt3(μ-PBut2)3(CO)2Cl (2) and ethynylferrocene, in the presence of catalytic amounts CuI, gives Pt3(μ-PBut2)3(CO)2C≡CFc (1), characterized by X-ray crystallography representing a rare example σ-coordination an alkynyl moiety to cluster unit. In dichloromethane (CH2Cl2) solution, compound 1 undergoes three consecutive one-electron oxidations, first which is assigned ferrocene-centered FeII/FeIII redox couple. Spectroelectrochemistry, carried out on solution 1, shows broad...
The first imidazolyl "upper-rim" derivatives of 1,3,5-triaza-7-phoshaadamantane (PTA), namely, 1-methylimidazolyl-(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6-yl)methanol (2, PTA-CH(1-MeIm)OH) and bis(1-methylimidazolyl)(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6-yl)methanol (3, PTA-C(1-MeIm)2OH), were synthesized in fair yields by reaction PTA-Li with 1-methyl-2-imidazole carboxyaldehyde bis(N-methylimidazole-2-yl) ketone, respectively. Compounds 2 3 exhibit higher water solubility...
The Ni6C(CO)9(AuPPh3)4 bimetallic carbide carbonyl cluster was obtained from the reaction of [Ni9C(CO)17]2– with Au(PPh3)Cl. It contains a rare carbon-centered (distorted) Ni6C octahedral core decorated by four Au(PPh3) fragments. These are μ3-bonded to contiguous Ni3-triangular faces and display weak intramolecular Au···Au d10–d10 interactions. has been characterized in solid state on two different solvato crystals, i.e., Ni6C(CO)9(AuPPh3)4·THF Ni6C(CO)9(AuPPh3)4·THF·0.5C6H14. solvates show...
The Co6C(CO)12(AuPPh3)4 carbide carbonyl cluster was obtained from the reaction of [Co6C(CO)15](2-) with Au(PPh3)Cl. This new species investigated by variable-temperature (31)P NMR spectroscopy, X-ray crystallography, and density functional theory methods. Three different solvates were characterized in solid state, namely, (I), Co6C(CO)12(AuPPh3)4·THF (II), Co6C(CO)12(AuPPh3)4·4THF (III), where THF = tetrahydrofuran. These are not merely same neutral cluster, but they contain three isomers...
A detailed mechanism of the I2-induced transformation white phosphorus into PI3 emerges from a DFT analysis. This multi-step process implies that at any stage one P-P and two I-I bonds cleavages, associated with formation P-I plus an in situ generated brand new I2 molecule. Significant electron transfer between atoms is observed step, but reactions are better defined as concerted rather than redox. Along steepest descent to product, no significant barrier encountered except for very first P4...