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Single Crystal X-ray Diffraction Analysis (single + crystal_x-ray_diffraction_analysis)
Selected AbstractsDehydrogenation of Hydridoirida-,-diketones in Methanol: The Selective Formation of Mono- and Dinuclear Acyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2010Roberto Ciganda Abstract The hydridoirida-,-diketone [IrH{(PPh2(o -C6H4CO))2H}Cl] (1) reacts with diimines (NN) or with pyridine (py) in refluxing methanol to undergo dehydrogenation. The reactions afford selectively the cis -acyl, trans -phosphane isomers of the cationic [Ir(PPh2(o -C6H4CO))2(NN)]+ {NN = 2,2,-bipyridine (2); R,N=C(CH3),C(CH3)=N,R, [R = R, = NH2 (3); R = R, = OH (4); R = OH, R, = NH2 (5)]} or neutral [IrCl(PPh2(o -C6H4CO))2(py)] (6) derivatives. The reactions are faster for ligands containing amino substituents. Refluxing 1 in MeOH affords the formation of an equimolar mixture of dimercationic species [Ir2(,-Cl)(,-PPh2(o -C6H4CO))2(PPh2(o -C6H4CO))2]+ (7a and 7b) containing two acyls and a chloride as bridging groups. The isomers could be separated by fractional precipitation. Compound [3]Cl, containing amino substituents in the imino functionalities, catalyses the hydrogen transfer from 2-propanol to cyclohexanone to afford cyclohexanol. All the complexes were fully characterised spectroscopically. Single crystal X-ray diffraction analysis was performed on complexes 6 and [7b]ClO4. [source] Synthesis, structure, and biological activity of novel 4,5-disubstituted thiazolyl urea derivativesHETEROATOM CHEMISTRY, Issue 1 2008Shao Ling Novel 1-(2,4-dichlorophenyl)-3-[4-aryl-5-(1H -1,2,4-triazol-1-yl)thiazol-2-yl] urea derivatives were synthesized by the reaction of 2-amino-4-sustituted phentyl-5-(1H -1,2,4-triazol-1-yl) thiazoles with 2,4-dichloro-1-isocyanatobenzene. Structures of the title compounds were confirmed by the elemental analysis, 1H NMR, and single crystal X-ray diffraction analysis. Biological evaluation showed that some of them possess promising antitumor activities. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:2,6, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20375 [source] Asymmetric Lithiation of Boron Trifluoride-Activated Aminoferrocenes: An Experimental and Computational InvestigationADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Costa Metallinos Abstract Tertiary aminoferrocenes complexed to boron trifluoride (BF3) are shown to undergo asymmetric lithiation with alkyllithiums in the presence of bulky chiral 1,2-diaminocyclohexane ligands. This reaction represents the first BF3 -activated asymmetric lithiation of a prochiral aromatic amine and the first such transformation to be mediated by a chiral diamine other than (,)-sparteine. The process provides rapid access to a broad range of enantiomerically enriched 2-substituted-1-aminoferrocenes, including derivatives with uncommon substitution patterns that are of interest in catalysis. The enantioselectivity of the process is high enough (87:13 to 91:9 er) to allow for isolation of single enantiomers of several products after simple recrystallization as either the free aminoferrocenes or their ammonium fluoroborate salts. Both antipodes of the planar chiral 2-substituted-1-aminoferrocene products are accessible, as confirmed by single crystal X-ray diffraction analysis of two compounds with opposite relative stereochemistry. Single-point calculation of thirty-two different transition states of the reaction at the M06-2X/6-311+g(2d,2p) level produced a computational model that correctly predicted both the sense and extent of chiral induction. Three factors appeared to play important roles in determining enantioinduction during lithiation of BF3 -complexed tertiary aminoferrocenes: (i) the maintenance of a highly organized eight-membered ring transition state; (ii) the existence of a strong Li,,,F contact which placed the chiral diamine ligand in close proximity to the ferrocene substrate; (iii) the orientation of the sterically demanding N -alkyl groups of the chiral diamine additives, either away or towards, the aminoferrocene and the alkyllithium. The model may serve as a predictive tool for the rational design of new ligands for this and related asymmetric lithiations. [source] Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of AlkanesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2010Telma F. Abstract The dioxovanadium(V) complexes [VO2(3,5-Me2Hpz)3][BF4] (1) (pz=pyrazolyl), [VO2{SO3C(pz)3}] (2), [VO2{HB(3,5-Me2pz)3}] (3) and [VO2{HC(pz)3}][BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)3] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me2pz)3] or 3,5-dimethylpyrazole (3,5-Me2Hpz; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)3], 2}, potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate {K[HB(3,5-Me2pz)3], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)3, 4], respectively. Treatment of [VO(OEt)3] with potassium hydrotris(1-pyrazolyl)borate {K[HB(pz)3]} led to the mixed ,3 -tris(pyrazolyl)borate and ,2 -bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)3}{H2B(pz)2}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%, TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions. [source] An efficient synthesis of polyhydroacridine derivatives by the three-component reaction of aldehydes, amines and dimedone in ionic liquidJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 3 2008Da-Qing Shi In this paper the preparation of 3,3,6,6-tetramethyl-9,10-diaryl-1,2,3,4,5,6,7,8,9,10-decahydroacridine-1,8-dione derivatives from aldehydes, aromatic amines and 5,5-dimethyl-1,3-cyclohexanedione in 1-n-butyl-3-methylimidazolium bromide ([bmim]Br) is described. The structures of these compounds were characterized by elemental analysis, IR and 1H NMR spectra and further confirmed by single crystal X-ray diffraction analysis. [source] Preparation and structures of a series of phosphorus-free Nickel(II) diamine complexes and their applications in hydrogenation of acetophenoneAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 9 2010Zilu Chen Abstract To develop economical and phosphorus-free catalysts for hydrogenation of ketones, three new complexes, [Ni(1R,2R -dpen)2(H2O)Cl]2Cl2· 2Et2O (1), [Ni(1R,2R -dpen)(phen)(CH3OH)2]Cl2·2CH3OH (2) and [Ni(1,8-dan)2(DMF)Cl]2Cl2· 3H2O (3), and three reported compounds, [Ni(opda)(phen)Cl2]·CH3OH (4), [Ni(opda)2Cl2] (5) and [Ni(1,2-dach)2]Cl2 (6), were prepared and the structures of new compounds were determined by single crystal X-ray diffraction analysis, in which 1R,2R -dpen, phen, 1,8-dan, opda and 1,2-dach denote 1R,2R -1,2-diphenylethylenediamine, 1,10-phenanthroline, 1,8-diaminonaphthalene, o -phenylenediamine and 1,2-diaminocyclohexane, respectively. The catalytic effects for hydrogenation of acetophenone of these compounds were tested. This revealed very poor or no catalytic effects of these complexes in transfer hydrogenation of acetophenone using isopropanol or HCOOHNEt3 as hydrogen source. However, they presented much better catalytic effects in ionic hydrogenation of acetophenone using H2 gas as hydrogen source with a dependence of the catalytic effects on the base used in the hydrogenation reactions. The complexes represent a kind of green hydrogenation catalyst, although the conversion in the hydrogenation reactions is not as high as expected. Copyright © 2010 John Wiley & Sons, Ltd. [source] Synthesis and characterization of transition metal complexes of thiophene-2-methylamine: X-ray crystal structure of palladium (II) and platinum (II) complexes and use of palladium(II) complexes as pre-catalyst in Heck and Suzuki cross-coupling reactionsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 11 2009Murat Aydemir Abstract The reactions of thiophene-2-(N -diphenylphosphino)methylamine, Ph2PNHCH2 -C4H3S, 1 and thiophene-2-[N,N -bis(diphenylphosphino)methylamine], (Ph2P)2NCH2 -C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2 -C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2 -C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2 -C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2 -C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P-, 13C-, 1H-NMR and IR spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X-ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross-coupling reactions. Copyright © 2009 John Wiley & Sons, Ltd. [source] Design, Synthesis and Insecticidal Activities of Novel N -Oxalyl Derivatives of Neonicotinoid CompoundCHINESE JOURNAL OF CHEMISTRY, Issue 3 2010Yu Zhao Abstract Ten novel neonicotinoid derivatives containing N -oxalyl groups were designed and synthesized, and their structures were characterized by 1H NMR, MS, IR, elemental analysis and single crystal X-ray diffraction analysis. The insecticidal activities of the new compounds were evaluated. The results of bioassays indicated that some of these title compounds exhibited excellent insecticidal activities. [source] Synthesis, Crystal Structure of Co(II)(6-methoxybenzothiazole- 2-carboxylate)2(DMF)2 and Its Application to Carbonylation of Benzyl ChlorideCHINESE JOURNAL OF CHEMISTRY, Issue 1 2010Bin Zhang Abstract A new complex, Co(MBTC)2(DMF)2 (MBTC=6-methoxybenzothiazole-2-carboxylate, DMF=N,N -dime- thylformamide), was synthesized in DMF solution and characterized by single crystal X-ray diffraction analysis. Using the cobalt complex as catalyst, phenylacetic acid was prepared by the carbonylation of benzyl chloride with carbon monoxide (0.1 MPa). The effects of solvents, phase transfer catalysts and temperature on the reactions were investigated. The yield of phenylacetic acid was higher than 90% in optimized condition. [source] Formation and Structure of an Anionic Ruthenaborane Compound: [Et4N][(PPh3)2ClRuB12H12]CHINESE JOURNAL OF CHEMISTRY, Issue 8 2009Yong NIE Abstract The title compound, [Et4N][(PPh3)2ClRuB12H12], was unexpectedly isolated from the reaction of RuCl2(PPh3)3 with closo -B10H102, in ethanol as a red air-stable solid, and characterized by IR and a single crystal X-ray diffraction analysis. Its formation results from the reaction of RuCl2(PPh3)3 and B12H122,, which was present as a byproduct in the preparation of B10H102,. It may be formally regarded as either a ruthenium(II) complex of closo -B12H122, via three B-H-Ru three-center two-electron bonds, or as a 13-vertex pileo2n -electron (n is the number of vertices) ruthenaborane cluster with a capped closo polyhedral skelecton. This is the first anionic and structurally characterized metal complex having a {RuB12H12} moiety. [source] Nickel(II) Complexes Bearing NH2CH2CH2CH2NH2 and o -C6H4(NH2)2 Ligands: Synthesis, Structures and Their Ethylene Polymerization BehaviorCHINESE JOURNAL OF CHEMISTRY, Issue 2 2009Xiaoming LU Abstract Two nickel complexes [Ni(NH2CH2CH2CH2NH2)3]Cl2 (1) and [Ni(C6H4N2H4)2Cl2] (2) have been obtained and characterized by IR and single crystal X-ray diffraction analysis. In complex 1, the nickel atom was in a chiral pseudo-octahedral [NiN6] geometry environment, which was coordinated by three 1,3-propylenediamine to form three six-membered rings. However in complex 2, besides connected with two o -phenylenediamine through four Ni,N bonds to form two five-membered rings, the nickel center was coordinated by two Cl to form trans -Ni-Cl2, which was different from general reported diimine nickel complexes. Activated with MAO, MMAO or Et2AlCl, these nickel complexes exhibited considerable good catalytic activity [up to 3.59×106 g·mol,1·h,1 for complex 2] for ethylene polymerization with main products as dimers or trimers of ethylene. [source] New Type of Polymeric Chain Constructed by Exo-bidentate Binaphthol DerivativeCHINESE JOURNAL OF CHEMISTRY, Issue 10 2005Ya-Qiong Gong Abstract The self-assembly of a racemic exo-bidentate ligand 2,2,-bis(4-pyridylmethyloxy)-1,1,-binaphthyl, namely Rac -L, with cadmium(II) salt gave rise to a new one-dimensional polymer, which has been characterized by single crystal X-ray diffraction analysis. The polymer crystallizes in a triclinic space group P -1 with unit cell parameters: a=0.6976(1) nm, b=1.30160(14) nm, c=1.71146(17) nm,,=105.141(3) °,,=94.263(5)°,,=100.405(4)°, V=1.4633(2) nm3, Z=2, C32H29CdCl2N2O4.5, M=696.88, Dc=1.584 g/cm3, F(000) =708, ,(Mo K,) =0.972 mm,1. The final R and wR are 0.0498 and 0.1282 for 5079 observed reflections with I,,(I). [source] Self-assembly of Two Novel Supramolecular Frameworks Based on Flexible Oligo- , -Pyridylamino Ligands and Copper(II) MaleateCHINESE JOURNAL OF CHEMISTRY, Issue 10 2005Cai-Hua Zhou Abstract Two novel supramolecular complexes, [Cu(bpapa)(mal)]·H2O·CH3OH (1) and {[Cu(bpapap)](Hmal)2}·2H2O (2) [bpapa=bis-[6-(2-pyridylamino)pyrid-2-yl]amine, bpapap=2,6-bis-[6-(pyrid-2-ylamino)pyrid-2-ylamino]-pyridine, mal=maleate dianion] were rationally designed and synthesized based on flexible multidentate ligands and copper(II) maleate. Complexes 1 and 2 were all characterized by elemental analysis, spectroscopic techniques, thermal analysis and single crystal X-ray diffraction analysis. Complex 1 is of an infinite 3-D supramolecular framework constructed by 2-D sheets to contain 1-D helical chains formed by intermolecular hydrogen bond interactions between the non-coordinated oxygen atoms from maleate and nitrogen atoms from amino groups of bpapa. Complex 2 also takes a 3-D supramolecular structure, which is built from 2-D rhombic sheets produced by sequential dimer units. Interestingly, three pairs of symmetrical hydrogen bonds generate these dimer units. [source] Asymmetric inducing synthesis of optically active tetrahedral cluster containing SMCOW coreCHINESE JOURNAL OF CHEMISTRY, Issue 7 2004Quan-Yi Zhao Abstract The chiral clusters (,3 -S)MCoW(CO)8[n5 -C5H4C(O)OCH3] =Ru (2), Fe (3)] were synthesized by asymmetric induction of N-benzylcinchonium chloride as phase-transfer catalyst (PTC). The most suitable amount of PTC is 70 mol%. Cluster 3 was determined by single crystal X-ray diffraction analysis. The best ee of the chiral cluster is over 20%. [source] Synthesis, Properties and Crystal Structure of Seven-coordinated Organotin Complex [nBu2Sn(OOCC5H4N-2)2(H2O)]CHINESE JOURNAL OF CHEMISTRY, Issue 12 2002Han-Dong Yin Abstract A novel seven-coordinated organotin complex [nBu2Sn-(OOCC5H4N-2)2(H2O)] was unexpectedly synthesized by reaction of nBu3SnCl with 2-pyridinecarboxylic acid in 1:1 molar ratio in the presence of organic base Et3N. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to rhombohedral with space group R-3c, a = 1.5807(3) nm, b = 1.5807(3) nm, c = 1.5807(3) nm, , = 105.717(2)°, , = 105.717(2)°, , = 105.717(2)°, Z = 6, V = 3.397(8) nm3, Dc = 1.452 g/cm3, , = 1.158 mm,1, F(000) = 1512, R1 = 0.0447, wR2 = 0.1038. In crystal, the tin atoms rendered seven-coordinate in a distorted pentagonal bipyramidal geometry. The two-dimensional network structure was formed by H-bonding interaction between the free oxygen atoms of carboxyl groups and the coordinated water molecules. [source] One-dimensional Infinite Chain Organotin Compounds: Synthesis and Structural Characterization of Triphenyltin Thiazole-2-carboxylate and Triphenyltin 3-PyridinylcarboxylateCHINESE JOURNAL OF CHEMISTRY, Issue 10 2002Han-Dong Yin Abstract Triphenyltin thiazole-2-carboxylate (1) and triphenyltin 3-pyridinylcarboxylate (2) were synthesized by the reaction of sodium thiazole-2-carboxylate or sodium 3-pyridinylcarboxylate with the triphenyltin chloride and their crystal structures were determined by single crystal X-ray diffraction analysis. In the structure of 1, the tin atom is five-coordinated in a distorted trigonal bipyramidal structure. Due to the presence of a close intermolecular Sn,S interaction distance of 0.3666 nm, the structure can be described as a weakly-bridged one-dimensional chain compound. In the structure of 2, the tin atom is five-coordinated with bridging 3-pyridinylcarboxylate ligands N atom and resulting structure is one-dimensional chain compound. [source] Preparation, Structural Characterization and Luminescent Property of Binuclear Silver (I) Complex Formed by Benzotriazole and 1-Hydroxymethyl BenzotriazoleCHINESE JOURNAL OF CHEMISTRY, Issue 9 2002Qing-Xiang Liu Abstract Dinuclear silver (I) six-membered ring complex [Ag2 (bta)2 -(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1-hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X-ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, , = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, , = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six-membered ring formed by two silver (I) atoms and four N-atoms from two benzotriazoles. The second structural feature of complex 3 is the ,-, stacking interaction between two adjacent molecular planes, which forms the two-dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement. [source] Reactions of the activated, rigid, ,-diazomethine group of 1,2,5-thiadiazole 1,1-dioxides with nitrogenated nucleophiles.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 4 2006Part III: aliphatic monoamines, phenylhydrazine Abstract The reactions of n -butylamine (BuNH2), 2-aminoethanol (H2N(CH2)2OH), diethylamine (Et2NH), and phenylhydrazine (PhN2H3) with 3,4-diphenyl-(1a) and phenanthro[9,10-c]-1,2,5-thiadiazole 1,1-dioxide (1b) were studied by cyclic voltammetry (CV) and 1H- and 13C-NMR in aprotic solvent solution. The course of the reactions depended on the substrate-nucleophile combination: Et2NH added to 1a or 1b, forming the corresponding thiadiazolines in an equilibrium monoaddition reaction. The equilibrium constants were evaluated and compared. With primary amines and PhN2H3, the nucleophile added to both CN double bonds of 1a and displaced the sulfamide moiety. In the case of the reaction of 1a with PhN2H3, the intermediate monoaddition thiadiazoline, 3-(2-phenylhydrazino)-3,4-diphenyl-1,2,5-thiadiazoline 1,1-dioxide, was also isolated. BuNH2 and H2N(CH2)2OH reacted with 1a to give ,-bis-imines, while 1a with PhN2H3 gave the ,-bis-hydrazone. The configurations of benzil bis(ethanolimine) and benzilosazone were determined by single crystal x-ray diffraction analysis as Z,Z. BuNH2 and PhN2H3 reduced 1b to the corresponding thiadiazoline compound 1bH2. Copyright © 2006 John Wiley & Sons, Ltd. [source] | ||||||||||