A5044454837- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Molecular Junctions and Nanostructures
- Organometallic Complex Synthesis and Catalysis
- Asymmetric Hydrogenation and Catalysis
- Carbon dioxide utilization in catalysis
- Organoboron and organosilicon chemistry
- Magnetism in coordination complexes
- Synthetic Organic Chemistry Methods
- Graphene research and applications
- Force Microscopy Techniques and Applications
- Catalytic Cross-Coupling Reactions
- Porphyrin and Phthalocyanine Chemistry
- Lanthanide and Transition Metal Complexes
- Crystallography and molecular interactions
- Semiconductor materials and devices
- Chemical Synthesis and Reactions
- Surface Chemistry and Catalysis
- Zeolite Catalysis and Synthesis
- Advanced NMR Techniques and Applications
- Organic Electronics and Photovoltaics
- Catalytic C–H Functionalization Methods
- Catalysis and Hydrodesulfurization Studies
- Advancements in Battery Materials
- Advanced Synthetic Organic Chemistry
Sapienza University of Rome
2016-2025
National Interuniversity Consortium of Materials Science and Technology
2008-2024
Provincia Autonoma di Trento
2024
German Cancer Research Center
2023-2024
Heidelberg University
2023-2024
STMicroelectronics (Italy)
2022-2023
Istituto Nazionale di Fisica Nucleare, Sezione di Firenze
2021
Consorzio Roma Ricerche
2020
Istituto Nazionale di Fisica Nucleare, Sezione di Roma I
2019
Northwestern University
2013-2019
Abstract Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs) 1–3 ultimately enhances device performance 4–7 . However, conventional strategies often rely on the use of highly reactive (strong) dopants 8–10 , which are consumed during process. Achieving efficient with weak and/or widely accessible under mild conditions remains a considerable challenge. Here, we report previously undescribed concept for...
The heterobimetallic complexes, (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-CnH2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-Cr(SNS); n 2, Ti-C2-Cr(SNS); 6, Ti-C6-Cr(SNS)), (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-C2H4-[N,N-bis((o-OMe-C6H4)2P)amine]CrCl3 (Ti-C2-Cr(PNP)), and (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine]CrCl3 (Ti-C2-Cr(NNN)), are synthesized, fully characterized, employed as olefin polymerization catalysts. With ethylene the feed MAO...
The synthesis, structural characterization, and ethylene polymerization properties of two neutrally charged Ni(II) phenoxyiminato catalysts are compared contrasted. Complex FI-SO2-Ni features a −SO2– group embedded in the ligand skeleton, whereas control FI-CH2-Ni has replaced by −CH2– functionality. In comparison with FI-CH2-Ni, at 25 °C, is 18 times more active, produces polyethylene 3.2 greater MW 1.5 branch content, significantly thermally stable. FI-SO2-Ni-derived polymer hyperbranched...
Tris[N,N-bis(trimethylsilyl)amide]lanthanum (LaNTMS) is an efficient and selective homogeneous catalyst for the deoxygenative reduction of tertiary secondary amides with pinacolborane (HBpin) at mild temperatures (25–60 °C). The reaction, which yields amines O(Bpin)2, tolerates nitro, halide, amino functional groups well, this amide completely selective, exclusion both competing inter- intramolecular alkene/alkyne hydroboration. Kinetic studies indicate that obeys unusual mixed-order rate...
Abstract Polyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to inert saturated hydrocarbon connectivities. Here very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on highly Brønsted acidic sulfated alumina support and characterized by broad array experimental theoretical techniques, is shown mediate the rapid hydrogenolytic cleavage molecular macromolecular...
A heterobimetallic catalyst, {Ti--Cr}, consisting of a constrained-geometry titanium olefin polymerization center (CGC(Et)Ti) covalently linked to chromium bis(thioether)amine ethylene trimerization (SNSCr) was synthesized and fully characterized. In homopolymerizations it affords linear low-density polyethylene with molecular weights as high 460 kg·mol(-1) exclusively n-butyl branches in conversion-insensitive densities ~18 branches/1000 carbon atoms, which are ~17 ~3 times...
Structural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically quite low. Here we report combined application solid-state (13)C-cross-polarization magic angle spinning nuclear magnetic resonance ((13)C-CPMAS-NMR) spectroscopy, density functional theory (DFT), and Zr X-ray absorption spectroscopy (XAS) to characterize adsorption products surface chemistry precatalysts...
The investigation of metal oxide/water interfaces at the molecular level represents a fundamental issue for understanding chemical, physical, and biological processes involved in several fields such as erosion, heterogeneous catalysis, prebiotic chemistry, corrosion, hygiene, or biocompatibility. In this context we have studied mineral (101) γ-AlOOH (boehmite) surface/water interface by means density functional theory based dynamics (DFT-MD). Boehmite is stepped surface, covered with...
Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), Al2O3 (AlS), and ZrO2–WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, Cp*ZrPh3 catalysts very active for benzene hydrogenation with activities declining decreasing acidity, ZrS ≫ AlS ≈ ZrW, arguing that more oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles this reason have higher activity. Benzene selective...
Tris[N,N-bis(trimethylsilyl)amido]lanthanum (LaNTMS) is an efficient, highly active, and selective homogeneous catalyst for ester reduction with pinacolborane (HBpin). Alkyl aryl esters are cleaved to the corresponding alkoxy- aryloxy-boronic which can then be straightforwardly hydrolyzed alcohols. Ester achieved 1 mol % loading at 25–60 °C, most substrates quantitatively reduced in h. Nitro, halide, amino functional groups well tolerated, completely chemoselective over potentially competing...
Homoleptic lanthanide trisamides provide a simple and highly accessible bridge between organolanthanide chemistry the synthetic methodology community, although they have proven to be competent catalysts in wide variety of unique transformations, their reactivity, scope, mechanism remain understudied relative metallocenes related organometallic catalysts. In this Perspective, we critical review recent advances homoleptic lanthanide-mediated catalysis as apply atom-efficient environmentally...
Importance Data on the association of COVID-19 vaccination with intensive care unit (ICU) admission and outcomes patients SARS-CoV-2–related pneumonia are scarce. Objective To evaluate whether is associated preventing ICU for to compare baseline characteristics vaccinated unvaccinated admitted an ICU. Design, Setting, Participants This retrospective cohort study regional data sets reports: (1) daily number administered vaccines (2) all consecutive in Lombardy, Italy, from August 1 December...
This contribution focuses on organolanthanide-mediated hydroamination processes and analyzes the hydroamination/cyclization of a prototypical aminoalkene, NH2(CH2)3CHCH2, catalyzed by Cp2LaCH(TMS)2, using density functional theory. The reaction is found to occur in two steps, namely, cyclization form La−C C−N bonds, subsequent protonolysis. Calculations have been carried out for (i) insertion olefinic moiety into La−N bond via four-center transition state (ii) protonolysis second substrate...
Hydrosilylation by H-terminated silicon of the double bond methyl 10-undecenoate with formation a robust SiC is first step in three-step procedure (see scheme) for anchoring single-molecule magnet (SMM) [Mn12O12(OAc)16(H2O)4] (1) on Si(100) surface.
This contribution focuses on the distinctive center-to-center cooperative catalytic properties exhibited by bimetallic "constrained geometry catalysts" (CGCs), and analyzes metal−metal proximity effects ethylene polymerization processes mediated (μ-CH2-3,3′){(η5-indenyl)[1-H2Si(tBuN)](ZrMe2)}2 (Zr2)-derived catalysts using density functional theory. Precatalyst geometries are first discussed, then ion-pair formation/heterolytic dissociation involving binuclear bis(borane) cocatalyst...
A supramolecular approach for the specific detection of sarcosine, recently linked to occurrence aggressive prostate cancer forms, has been developed. hybrid active surface was prepared by covalent anchoring on Si substrates a tetraphosphonate cavitand as receptor and it proven able recognize sarcosine from its nonmethylated precursor, glycine, in water urine. The entire complexation process investigated solid state, solution, at solid-liquid interface determine weight all factors...
Abstract The single‐site supported organozirconium catalyst Cp*ZrBz 2 /ZrS (Cp*=Me 5 C , Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single‐face/all‐cis hydrogenation of a large series alkylated and fused arene derivatives to corresponding all‐cis‐cyclohexanes. Kinetic/mechanistic DFT analysis argue that stereoselection involves rapid, sequential H delivery single catalyst‐bound face, versus any competing intramolecular π‐face interchange.
Homobimetallic Hf(IV) complexes, L2-Hf2Me5 (3) and L2-Hf2Me4 (4) (L2 = N,N′-{[naphthalene-1,4-diylbis(pyridine-6,2-diyl)]bis[(2-isopropylphenyl)methylene)]bis(2,6-diisopropylaniline}), were synthesized by reaction of the free ligand L2 with appropriate Hf precursor characterized in solution (NMR) solid state (X-ray diffraction). In 3, acts as a dianionic tridentate for one metal center monoanionic bidentate other, whereas 4, both units are tricoordinated to opposite sides L2. state, Hf···Hf...
In principal, the direct copolymerization of ethylene with polar comonomers should be most efficient means to introduce functional groups into conventional polyolefins but remains a formidable challenge. Despite tremendous advances in group 4-centered catalysis for olefin polymerization, successful examples + monomer are rare, especially without Lewis acidic masking reagents. Here we report that certain 4 catalysts very effective CH2 =CH(CH2 )n NR2 copolymerizations activities up 3400 Kg...