Search results for "Oro"

Protonation and Electrochemical Properties of Pyridyl- and Sulfonatophenyl-Substituted Porphyrins in Nonaqueous Media

2017

International audience; The protonation and electrochemical properties of positively charged and negatively charged porphyrins are reported in up to five different nonaqueous solvents. The positively charged porphyrins are represented by mono- and di-pyridyl derivatives having the formula Pyx(PhMe)4-xPM, where P=the dianion of the porphyrin macrocycle, PhMe is a meso-tolyl group, Py a meso-pyridyl group, x=1 or 2, and M=H2, NiII, CuII, ZnII, or CoII. The negatively charged porphyrins are comprised of meso-tetrasulfonato derivatives having the formula [(R)4(TPPS)H2]4−(X+)4, where [(TPPS)H2]4− represents the porphyrin with four SO3− groups on the meso-phenyl substituents of the macrocycle, R=…

Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

2018

Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…

Effect of Guest Molecules on Spin Transition Temperature in Loaded Hofmann‐Like Clathrates with Improved Porosity

2020

The synthesis, crystal structure, magnetic and calorimetric studies of a new clathrate compound of the Hofmann-type spin crossover (SCO) metal-organic framework (MOF) {Fe(bpb)[MII(CN)4]}·xGuest (bpb = bis(4-pyridyl)butadiyne, and MII = Ni, Pt) with characteristic fsc topology is reported. The framework {Fe(bpb)[MII(CN)4]} can host up to 1.5 guest molecules of (trifluoromethyl)benzene and display complete one-step cooperative SCO behavior. Our systematic study on {Fe(bpb)[Pt(CN)4]}·xGuest shows a general reciprocal correlation between the SCO temperature with the volume of the guest molecules.

Tuning the Electronic Properties of the Dative N-B Bond with Associated O-B Interaction: Electron Localizability Indicator from X-Ray Wavefunction Re…

2016

Despite the immense growth in interest in difluoroborate dyes, the nature of the interactions of the boron atom within the N-BF2 -O kernel is not yet fully understood. Herein, a set of real-space bonding indicators is used to quantify the electronic characteristics of the dative N-B bond in difluoroborate derivatives. The atoms-in-molecules (AIM) partitioning scheme is complemented by the electron localizability indicator (ELI-D) approach, and both were applied to experimental and theoretical electron-density distributions (X-ray constrained wavefunction fitting vs. DFT calculations). Additionally, Fermi orbital analysis was introduced for small DFT models to support and extend the findings…

Sequential Nucleophilic−Electrophilic Reactions Selectively Produce Isomerically Pure Nona‐ B ‐Substituted o ‐Carborane Derivatives

2003

Nine equal substituents on the intensively studied o-carborane have been obtained for the first time by a combined nucleophilic-electrophilic reaction sequence. Iodine and methyl groups have been introduced to prove the generality of the method. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Oxotris(oxalate)niobate(V): An oxalate delivery agent in the design of building blocks

2018

This work concerns the oxalate delivery process that occurs when using (NH4)3[NbO(C2O4)3]·6H2O as a suitable oxalate source in the synthesis of two compounds, [Cu(dmphen)(C2O4)(H2O)] (1) and [{Cu(dmphen)(CH3OH)}2(μ-C2O4)](ClO4)2 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline). {[Fe{HB(pz)3}(CN)2(μ-CN)]2[{Cu(dmphen)}2(μ-C2O4)]}∙xCH3OH (3) (2.0 ≤ x ≤ 2.4) was obtained by reacting 2 and PPh4[Fe{HB(pz)3}(CN)3]∙H2O [ = tetraphenylphosphonium and = tris(pyrazolyl)borate]. Crystal structures of 1–3 have been determined by single-crystal X-ray diffraction experiments: 1 is a mononuclear trigonal bipyramidal copper(II) species, 2 is a centrosymmetric oxalato-bridged dicopper(II) complex, and 3 consi…

Structurally characterized dipalladium(ii)-oxamate metallacyclophanes as efficient catalysts for sustainable Heck and Suzuki reactions in ionic liqui…

2018

A new generation of dipalladium-oxamate metallacyclophanes of formulas (n-NBu4)4 [Pd2(ppba)2] (1), (n-NBu4)4[Pd2(dpvba)2] (2), (n-NBu4)4[Pd2(dpazba)2] (3), (n-NBu4)4[Pd2(dpeba)2] (4) and (n-NBu4)4[Pd2(tpeba)2] (5) [n-NBu4+ = tetra-n-butylammonium cation, H4ppba = N,N′-1,4-phenylenebis(oxamic acid), H4dpvba = N,N′-4,4′-diphenylethenebis(oxamic acid), H4dpazba = N,N′-4,4′-diphenylazobis(oxamic acid), H4dpeba = N,N′-4,4′-diphenylethynebis(oxamic acid) and H4tpeba = N,N′-1,4-di(4-phenylethynyl)phenylenebis(oxamic acid)] was prepared. The crystal structure of the solvated species of 2–4, namely (n-NBu4)4[Pd2(dpvba)2]·6MeOH·2Et2O (2a), (n-NBu4)4[Pd2(dpazba)2]·8MeOH (3a), and (n-NBu4)2[Pd2(dpeba)2…

Automated Diffraction Tomography for the Structure Elucidation of Twinned, Sub-micrometer Crystals of a Highly Porous, Catalytically Active Bismuth M…

2012

A novel two-dimensional organostannoxane coordination network promoted by phenazine: Synthesis, characterization and X-ray structure of

2009

Abstract Reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(μ-OH)(H2O)0.5(η1-O3SCF3)]2 (1) with phenazine (C12H8N2, Phz) (2) in dichloromethane at room temperature in a 1:3 molar ratio yielded the novel two-dimensional organometallic coordination polymer 2 ∞ { [ n - Bu 2 ( μ -OH ) SnOSn ( μ - η 2 - O 3 SCF 3 ) n - Bu 2 ] 2 [ n - Bu 2 ( μ -OH ) SnOSn ( η 1 - O 3 SCF 3 ) n - Bu 2 ] 2 } (3), together with the phenazinium trifluoromethanesulfonate salt [C12H9N2]+ [CF3SO3]−, crystallographically isolated in two different structural arrangements, free 4 and in π–π aromatic stacking interaction with independent intercalated non-protonated phenazine molecu…

Photolysis of Tertiary Amines in the Presence of CO2: The Paths to Formic Acid, α-Amino Acids, and 1,2-Diamines

2017

The photolysis of triethylamine (1a) in the presence of carbon dioxide leads to the hydrogenation of CO2, the α-C-C coupling of triethylamine (1a), and the CO2-insertion into the α-C-H σ-bond of amine 1a. This reaction is proposed to proceed through the radical ion pair [R3N·+·CO2·-] generated by the photoionization of amine 1a and the electron capture by CO2. The presence of lithium tetrafluoroborate in the reaction medium promotes the efficient and stereoselective α-C-C coupling of 1a by enhancing the production of α-dialkylamino radicals and the isomerization of N,N,N',N'-tetraethylbutane-2,3-diamine (4a).