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A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state
PublicationPrzedmiotem studiów jest chemia koordynacyjna solwatów jonów wanadu(III), oksowanadu(IV) jaki i dioksowanadu(V) w rozpuszczalnikach tlenowo-donorowych takich jak: woda, dimetylosulfotlenek (DMSO) oraz N,N'-dimetylopropylenomocznik (DMPU). Badania prowadzone były w roztworach ciekłych jak i w fazie stałej z wykorzystaniem absorpcji (EXAFS), rozproszenia (LAXS) jak i dyfrakcji promieniowania X. Analiza uzyskanych wyników wskazuje,...
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The structure of dimethylsulfoxide-solvated magnesium and calcium ions in solution and the solid state, and overview of the coordination chemistry of hydrated and solvated alkaline earth metal ions
PublicationOznaczono strukturę w stanie stałym i ciekłym solwatowanych jonów magnezu i wapnia w dimetylosulfotlenku. Stwierdzono, ze jony te tworzą sześciokoordynacyjne solwaty ze średnią długością wiązań Mg-O i Ca-O 2.062(4) i 2.303(5)A. Przegląd literaturowy ukazał, że jony berylu i magnezu we wszystkich rozpuszczalnikach tworzą odpowiednio cztero- i sześciokoordynacyjne solwaty, podczas gdy jony wapnia i strontu istnieją jako ośmiokoordynacyjne...
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Analysis and characterization of coordination compounds by resonance Raman spectroscopy
PublicationResonance Raman spectroscopy has become a powerful tool to study excited-state geometries, excited-state charge distributions and photoinduced reaction dynamics in coordination compounds. Due to their rich photophysical properties coordination compounds are utilized for a variety of applications ranging from DNA sensing to photocatalysis. This review features recent applications of various resonance Raman scattering techniques...
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Copper(I) π-coordination compounds with allyl derivatives of disubstituted pseudothiohydantoin: synthesis, structure investigation and nonlinear optical features
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Functionality stored in the structures of cyclodextrin–porphyrinoid systems
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Mechanistic studies of the hydrolysis of p-nitrophenyl sulfate catalyzed by arylsulfatase from Helix pomatia
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Alcohol dehydrogenase and its simple inorganic models
PublicationW pierwszej części pracy przeglądowej przedstawiono aktualny stan wiedzy nt mechanizmu działania zależnej od cynku dehydrogenazy alkoholowej. Następnie omówiono dane strukturalne i spektroskopowe uzyskane przy pomocy prostych związków modelowych - na ogół tiolanów cynku i niektórych innych metali przejściowych. Opisano również próby zastosowania prostych kompleksów nieorganicznych naśladujących budowę miejsca aktywnego dehydrogenazy...
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Vanadium complexes with salicylaldehyde-based Schiff base ligands—structure, properties and biological activity
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Complexes of silanethiolate ligands: Synthesis, structure, properties and application
PublicationThe purposeful syntheses of silanethiolate complexes started approximately in the mid-eighties of the 20th century but no summary of the synthetic efforts has been reported till now. The synthetic methods and the resulting complexes have some common features, which are emphasized throughout the review. Thereby specific difficulties during synthesis are outlined and the structures, properties and possible applications of the resulting...
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Selective adsorption of BTEX on calixarene-based molecular coordination network determined by 13C NMR spectroscopy
PublicationBenzene, toluene, ethylbenzene, and xylenes (BTEX), a class of volatile organic compounds, are harmful pollutants but also very important precursors in organic industrial chemistry. Among different approaches used for the BTEX treatment, the adsorption technology has been recognized as an efficient approach because it allows to recover and reuse both adsorbent and adsorbate. However, the selective adsorption of the components is...
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Overview of the Synthesis and Catalytic Reactivity of Transition Metal Complexes Based on C═P Bond Systems
PublicationThis report provides an overview of the use of phosphaalkenes (C=P) in syntheses of various complexes. Going through successive complexes containing the d-block metals, we sought how this area of chemistry was formed over the years. Additionally, this work contains information on the possible coordination types and means of constructing the complexes. In addition, this review reveals the reactivities of phosphaalkene complexes...
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On the Structure and Volumetric Properties of Solvated Lanthanoid(III) Ions in Amide Solutions
PublicationThe coordination chemistry and the volumetric properties of three representative lanthanoid(III) ions lanthanum-(III), gadolinium(III), and lutetium(III) have been studied in three amide solvents with gradually increasing spatial demand upon coordination: N,N-dimethylformamide (dmf)
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Exploring novel Cd(ii) complexes with 5-methyl-4-imidazolecarboxaldehyde: synthesis, structure, computational insights, and affinity to DNA through switchSense methodology
PublicationA series of four Cd(II) complexes with 5-methyl-4-imidazolecarboxaldehyde (L) with different inorganic anions within or outside the coordination sphere of general formula: [CdCl2 L2 ] (1), [CdBr2 L 2] (2), [CdI2L 2] (3), and [CdL4 ](PF6 )2 ·3H2 O (4) was synthesized through one-step and two-step reactions, respectively. All complexes were obtained as colorless crystals without the need for recrystallization and exhibited solubi- lity...
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Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles in the Presence of Heterogeneous Catalyst
PublicationTetrazoles are five-membered heterocyclic compounds containing in their rings four nitrogen atoms. They have wide applications as corrosion inhibitors, analytical reagents, high-energy materials and gas generating compositions. Tetrazoles also play important role in coordination chemistry as ligands and in medicinal chemistry as metabolically stable surrogates for carboxylic acids. In recent years, investigation of new method of...
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Exploring thiophene-2-acetate and thiophene-3-acetate binding modes towards the molecular and supramolecular structures and photoluminescence properties of Pb(ii) polymers
PublicationTo evaluate the impact of the flexible positional isomeric ligands thiophene-2-acetate (2tpacCOO) andthiophene-3-acetate (3tpacCOO) on the construction and self-assembly process of Pb(II) polymers, twonovel compounds, [Pb(2tpacCOO)2(H2O)]n(1) and [Pb(3tpacCOO)2]n(2), were preparedviaanonhydro-thermal method with respect to green chemistry rules. The obtained polymers were fully characterized byelemental analysis, TG/DTG and PXRD,...
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Porphyrazines Peripherally Functionalized with Hybrid Ligands as Molecular Scaffolds for Bimetallic Metal-Ion Coordination
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Nonconventional 1,8-Diazafluoren-9-One Aggregates for Green Light Enhancement in Hybrid Biocompatible Media
PublicationOrganic aggregates currently play a prominent role, mainly for their unique optoelectronic properties in the aggregated state. Such properties can be related to the aggregates’ structure and the molecular packing mode. In the literature, we have well-established models of H and J aggregates defined based on the molecular exciton model. However, unconventional aggregates, the most unrecognized forms, have been generating interest...
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Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers
PublicationThe organic ligand 2,5-piperazinedione-1,4-diaceticacid (H2PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P21/c space group as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric...
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Thermostability and photophysical properties of mixed-ligand carboxylate/benzimidazole Zn(II)-coordination polymers
PublicationThe reaction between Zn(NO3)2*6H2O or Zn(CH3COO)2*2H2O and isophthalic acid (1,3-H2bdc) in the presence of benzimidazole (Hbzim) in dimethylformamide (DMF)/ethanol (EtOH)/H2O solvent mixture at room temperature yielded two structurally different coordination polymers: [Zn2(1,3-bdc)2(Hbzim)2] (1) and [Zn2(1,3-bdc)(bzim)2] (2). (1) is a 2D-layered framework with a molecule of benzimidazole coordinated to the Zn center, whereas (2)...
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Broad-Range Spectral Analysis for Chiral Metal Coordination Compounds: (Chiro)optical Superspectrum of Cobalt(II) Complexes
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Benzene-induced hydro(solvo)thermal synthesis of Cu2+ and Zn2+ coordination polymers based on 1,3-benzenedicarboxylate
PublicationHydro(solvo)thermal reactions of Cu(NO3)2·2.5H2O or Zn(NO3)2·6H2O with 1,3-H2bdc provided two structurally different coordination polymers; a 2D network “metallacalixarene” based on the paddlewheel-type cluster with the formula [Cu(1,3-bdc)·H2O]·H2O (1) and a 3D framework [Zn(1,3-bdc)] (2), respectively. The use of a base was unnecessary in this synthesis; however, the presence of benzene played a crucial role in the crystallization...
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Lead(II) coordination polymers with imidazole-4- and pyrazole-3-carboxylate isomeric linkers: Structural diversity and luminescence properties
PublicationUsing 1H-imidazole-4-carboxylic acid (4imCOOH) and 1H-pyrazole-3-carboxylic acid (3pyrCOOH) coordination polymers [Pb(4imCOO)2(H2O)]n (1) and [Pb2(3pyrCOO)4]n (2) were constructed. Obtained polymers were characterized via FT-IR, X-ray, PL and TG methods. The coordination polyhedron around Pb(II) in 1 is described as distorted pentagonal pyramid with hemidirected coordination sphere (based on DFT calculations). Compound 2 consists...
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Evidence of Ligand Elasticity Occurring in Temperature-, Light-, and Pressure-Induced Spin Crossover in 1D Coordination Polymers [Fe(3ditz)3]X2(X = ClO4-, BF4-)
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Structural Variety of Cobalt(II), Nickel(II), Zinc(II), and Cadmium(II) Complexes with 4,4′-Azopyridine: Synthesis, Structure and Luminescence Properties
PublicationSelf-assembled bi- and polymetallic complexes of CoII, NiII, ZnII, and CdII were obtained by the reaction of 4,4′-azopyridine (azpy) with metal tri-tert-butoxysilanethiolates (Co, 1; Cd, 2), acetylacetonates (Ni, 3; Zn, 4), and acetates (Cd, 5). All compounds were characterized by single-crystal X-ray structure analysis, elemental analysis, FTIR spectroscopy, and thermogravimetry. Complexes 1, 2 and 4, 5 exhibit diverse structural...
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Synthesis, Structure, and Spectroscopic Properties of Calcium Thiophenecarboxylate Polymers. Structural Comparison with Analogous Lead Complexes
PublicationThree novel calcium coordination polymers [Ca(2tpCOO)2(2mpa)(H2O)]n (1), [Ca(3tpCOO)2(2mpa)(H2O)]n (2), and {[Ca(3tpacCOO)2(H2O)2]⋅⋅⋅H2O}n (3) (2tpCOO− or 3tpCOO− – thiophene-2- or thiophene-3-carboxylate, 3tpacCOO− – thiophene-3-acetate, 2mpa – 2-methylpropanal), were synthesised using a self-assembly method. The obtained polymers were characterised using SC-XRD, FTIR, UV-Vis DRS, thermogravimetric and luminescence analyses. The...
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Silver(I) complexes with nitrile ligands: New materials with versatile applications
PublicationIn the present study, the structure, thermal stability, conductive properties, and antimicrobial activity of silver(I) complexes with nitrile ligands were investigated. For the construction of the materials, 2-cyanopyridine (2-cpy), 4-cyanopyridine (4-cpy), 1,2-dicyanobenzene (1,2-dcb), and 1,3-dicyanobenzene (1,3-dcb) were used in addition to the silver nitrite and nitrate. Four new compounds were isolated and structurally characterized:...
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Novel luminescent calixarene-based lanthanide materials: From synthesis and characterization to the selective detection of Fe3+
PublicationCalix[n]arene-based coordination networks are an emerging class of materials with intriguing properties resulted from the presence of the cavity-like structure of the macrocycle and metallic nodes. In this work, four novel luminescent materials based on calix[4]arene-carboxylate and lanthanides (Eu3þ and Tb3þ) were prepared by two synthetic approaches, solvothermal (CDA-Eu-ST) and slow diffusion (CDA-Eu-RT, CDA-Tb-RT, CTA-Tb-complex)...
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Procognitive activity of nitric oxide inhibitors and donors in animal models
PublicationNitric oxide is a small gaseous molecule that plays important roles in the majority of biological functions. Impairments of NO-related pathways contribute to the majority of neurological disorders, such as Alzheimer’s disease (AD), and mental disorders, such as schizophrenia. Cognitive decline is one of the most serious impairments accompanying both AD and schizophrenia. In the present study, the activities of NO donors, slow (spermine...
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Probing the Magnetic Anisotropy of Co(II) Complexes Featuring Redox-Active Ligands
PublicationCoordination complexes that possess large magnetic anisotropy (otherwise known as zero-field splitting, ZFS) have possible applications in the field of magnetic materials, including single molecule magnets (SMMs). Previous studies have explored the role of coordination number and geometry in controlling the magnetic anisotropy and SMM behavior of high-spin (S = 3/2) Co(II) complexes. Building upon these efforts, the present work...
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On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents
PublicationThe structures of the N,N-dimethylformamide (dmf), N,N-dimethylacetamide (dma), and N,N-dimethylpropionamide (dmp) solvated strontium and barium ions have been determined in solution using large angle X-ray scattering and EXAFS spectroscopy. The strontium ion has a mean coordination number (CN) between 6.2 and 6.8, and the barium ion has a mean CN between 7.1 and 7.8 in these amide solvents. The non-integer numbers indicates that...
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Ultrafast Intramolecular Relaxation and Wave-Packet Motion in a Ruthenium-Based Supramolecular Photocatalyst
PublicationThe hydrogen-evolving photocatalyst [(tbbpy)2 Ru(tpphz)Pd(Cl)2 ](2+) (tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, tpphz=tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) shows excitation-wavelength-dependent catalytic activity, which has been correlated to the localization of the initial excitation within the coordination sphere. In this contribution the excitation-wavelength dependence of the early excited-state relaxation...
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The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes
PublicationThe reactivities of phosphanylphosphinidene complexes [(DippN)2W(Cl)(η2-P−PtBu2)]− (1), [(pTol3P)2Pt(η2- P=PtBu2)] (2), and [(dppe)Pt(η2-P=PtBu2)] (3) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex (1) with stochiometric Br(CH2)nBr (n = 3, 4, 6) led to the formation of neutral complexes with a tBu2PP(CH2)3Br ligand or neutral dinuclear complexes with unusual tetradentate...
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Assestment of the anti-cancer activity of the copper complexes with imidazole and pivalato ligands
PublicationDespite the development of science and technology progress so far there have not been found effective drugs for cancer. Many coordination compounds were investigated due to their antitumor potential. The most known cis-diamminedichloroplatinum(II) is used as anti-cancer therapeutic agent. The copper complexes are the coordination compounds possessing anti-tumour properties. Their capability to kill cancer cells is mainly linked...
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Anticancer Study on IrIII and RhIII Half-Sandwich Complexes with the Bipyridylsulfonamide Ligand
PublicationTwo non-platinum compounds, organometallic half-sandwich complexes [(η 5 -Cp)IrCl(L)]PF 6 (1) and [(η 5 -Cp)RhCl(L)]PF 6 (2) were prepared by treating pentamethylcyclopentadienyl chloride dimers of iridium(III) or rhodium(III) with the obtained 4-amino-N-(2,2'-bipyridin-5- yl)benzenesulfonamide ligand (L) and ammonium hexafluorophosphate. The crystal structures of ligand (L) and complexes 1 and 2 were obtained and then analyzed. Coordination...
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Investigation of the structural and thermal properties of aluminum-rich Ca–Al–Si–O–N glasses
PublicationIn this paper, we investigate the structure and thermal properties of aluminum-rich transparent Ca–Al–Si–O–N glasses. The obtained glasses were prepared by a traditional melt-quenching technique at 1650 °C using AlN as the nitrogen source. The obtained glasses have a nAl/nSi>1 and contain up to 17 eq.% of N. The structure of the glasses was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, infrared, and Raman...
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Local Structure and Stability of SEI in Graphite and ZFO Electrodes Probed by As K-edge Absorption Spectroscopy
PublicationThe evolution of the solid electrolyte interphase (SEI) during the first Li uptake in advanced Li-ion electrodes is studied by X-ray absorption spectroscopy (XAS). The As atoms present in the electrolyte solution were used as a local probe for monitoring the SEI growth on different electrodes. High-quality As K-edge spectra were collected in fluorescence mode for a set of graphite and carbon-coated ZnFe2O4 electrodes. XAS measurements...
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Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes
PublicationThis work describes a series of iron(II) phosphanylphosphido complexes. These compounds were obtained by reacting lithiated diphosphanes R2PP(SiMe3)Li (R = t-Bu, i-Pr) with an iron(II) β-diketiminate complex, [LFe(μ2-Cl)2Li(DME)2] (1), where DME = 1,2-dimethoxyethane and L = Dippnacnac (β-diketiminate). While the reaction of 1 with t-Bu2PP(SiMe3)Li yields [LFe(η1-Me3SiPPt- Bu2)] (2), that of 1 with equimolar amounts of i-Pr2PP(SiMe3)Li,...
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An unusual four-nuclear Pb(II)-pyrrole-2-carboxylato polymer: The effect of the lone pair and non-covalent interactions on the supramolecular assembly and fluorescence properties
PublicationThe reaction of Pb(NO3)2 with 1H-pyrrole-2-carboxylic acid (2prCOOH) leads to the formation of a new four-nuclear Pb(II) polymer, [Pb4(2prCOO)8(H2O)]n, which has been characterized by CHN, FT-IR, TG, PL and single-crystal X-ray diffraction methods. In view of the primary Pb–O bonds, Pb1 and Pb3 show hemidirected pentagonal pyramidal geometries, while Pb2 and Pb4 display hemidirected octahedral geometries. The topology of the strongest...
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Crystallographic study of self-organization in the solid state including quasi-aromatic pseudo-ring stacking interactions in 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea and 1-benzoyl-3-(2-hydroxypropyl)thiourea
Publication1-Benzoylthioureas contain both carbonyl and thiocarbonyl functional groups and are of interest for their biological activity, metal coordination ability and involvement in hydrogen-bond formation. Two novel 1-benzoylthiourea derivatives, namely 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea, C₁₆H₁₆N₂O₃S, (I), and 1-benzoyl-3-(2-hydroxypropyl)thiourea, C₁₁H₁₄N₂O₂S, (II), have been synthesized and characterized. Compound (I) crystallizes...
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Copper(I) iodide ribbons coordinated with thiourea derivatives
PublicationTwo products of the reactions of CuI with 1-benzoyl-3-(4-bromophenyl)thiourea and with 1-benzoyl-3-(2-iodophenyl)thiourea have been obtained and characterized, namely poly[[[1-benzoyl-3-(4-bromophenyl)thiourea-κS]-µ3-iodidocopper(I)] acetone hemisolvate], {[CuI(C₁₄H₁₁BrN₂OS)]‧0.5C₃H₆O}ₙ, and poly-[µ₄-iodido-µ₃-iodido-[N-(benzo[d]thiazol-2-yl)benzamide-κN]dicopper(I)], [Cu₂I₂(C₁₄H₁₀N₂OS)]ₙ. Their structures, determined by single-crystal...
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Phosphanylphosphido and phosphanylphosphinidene complexes of zirconium(IV) supported by bidentate N,N ligands
PublicationPhosphanylphosphido complexes of zirconium, [NacNacZrCl2(η2-R2P–PSiMe3)] (R = t-Bu, i-Pr), were synthesized in the reaction of R2P–P(SiMe3)Li·nTHF (R = t-Bu, i-Pr) with a β-diketiminate complex, [NacNacZrCl3], in toluene. Elimination of Me3SiCl from [NacNacZrCl2(η2-R2P–PSiMe3)] provided the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)] (R = t-Bu, i-Pr). Moreover, the reaction of [NacNacZrCl2(η2-R2P–PSiMe3)] with R2P–P(SiMe3)Li·nTHF...
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Reactions of lithiated diphosphanes R2P-P(SiMe3)LiTHF (R = tBu, iPr) with [(PNP)TiCl2]. Two different coordination types of phosphanylphosphido ligand to the metal center.
Publication[(PNP)TiCl2] (PNP = N[2-PiPr2-4-methylphenyl]2) reacts with one equivalent of lithium derivative of diphosphane R2P-P(SiMe3)LinTHF (R = tBu, iPr) in toluene and forms the first complex with g1-coordination [(PNP)Ti(Cl){g1-P(SiMe3)-PtBu2}] (1) and complex with g2-coordination [(PNP)Ti(Cl){g2-P(SiMe3)-PiPr2}] (2) of phosphanylphosphido ligands to the titanium center. The similar reaction with two equivalents of tBu2P-P(SiMe3)LinTHF...
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Synthesis of compounds with C-P-P and C=P-P bond systems based on the phospha-Wittig reaction
PublicationA reactivity study of a β-diketiminate titanium(III) phosphanylphosphido complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}] (1) towards ketones such as benzophenone, 9-fluorenone, acetophenone, cyclopentanone, cyclohexanone and cycloheptanone is reported. The reactions of 1 with aromatic ketones (without α-protons) directly lead to the Ti(III) complex [MeNacNacTi(μ2-Cl)(OSiMe3)] (5) as well as Ti(IV) complexes with the pinacol condensation...
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Reactivity study of a β-diketiminate titanium(III) complex with a phosphanylphosphido ligand towards chlorophosphanes. A new method of synthesis of β-diketiminate titanium(IV) complexes with versatile phosphanylphosphinidenes
PublicationThe reactivity of ab-diketiminate titanium(III) complex with a phosphanylphosphido ligand, [MeNacNacTi(Cl){g2-P(SiMe3)-PtBu2}] (1)(MeNacNac= [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2Ph), was investigatedtowards selected chlorophosphanes, such astBu2PCl,iPr2PCl, Cy2PCl, (Cy)tBuPCl, (Me)tBuPCl, (Ph)tBuPCl, Ph2PCl, (iPr2N)tBuPCl and (Et2N)2PCl. The reactions withtBu2PCl and Ph2PCl lead mainly to theearlier described complex [MeNacNacTi(Cl){g2-P-PtBu2}]...