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841.
Philip J. Bailey Dr. Laura Budd Dr. Filipa A. Cavaco Simon Parsons Prof. Felix Rudolphi Alejandro Sanchez‐Perucha Dr. Fraser J. White Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(9):2819-2829
The dimethylamine in the adducts [(HNMe2)B(azolyl)3] (azolyl=methimazolyl, pyrazolyl), obtained by reaction of the azole with B(NMe2)3, can readily be substituted with a range of nitrogen donors to provide new charge‐neutral, tripodal ligands in high yield. This observation has led to a revision of an earlier interpretation of the mechanism of the formation of these species. The donor properties of the ligands [(nmi)B(azolyl)3] (nmi=N‐methylimidazole) have been compared with their anionic analogues [HB(azolyl)3]? by synthesis of their manganese(I)–tricarbonyl complexes and comparison of their infrared νCO energies. This comparison indicates that the new neutral ligands are only marginally weaker donors than the corresponding anionic hydrotris(azolyl)borate ligands. This may be explained by the ability of the attached nmi ring to stabilize a positive charge remotely from the coordinated metal, which may also account for the fact that the [(nmi)B(pyrazolyl)3] ligand is a substantially stronger donor than the similarly neutral tris(pyrazolyl)methane ligand. 相似文献
842.
Tina Osswald Antonio Mezzetti Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(4):1388-1397
The like and unlike isomers of phosphoramidite (P*) ligands are found to react differently with iridium(I), which is a key to explaining the apparently inconsistent results obtained by us and other research groups in a variety of catalytic reactions. Thus, the unlike diastereoisomer (aR,S,S)‐[IrCl(cod)( 1 a )] ( 2 a ; cod=1,5‐cyclooctadiene, 1 a =(aR,S,S)‐(1,1′‐binaphthalene)‐2,2′‐diyl bis(1‐phenylethyl)phosphoramidite) forms, upon chloride abstraction, the monosubstituted complex (aR,S,S)‐[Ir(cod)(1,2‐η‐ 1 a ,κP)]+ ( 3 a ), which contains a chelating P* ligand that features an η2 interaction between a dangling phenyl group and iridium. Under analogous conditions, the like analogue (aR,R,R)‐ 1 a′ gives the disubstituted species (aR,R,R)‐[Ir(cod)( 1 a′ ,κP)2]+ ( 4 a′ ) with monodentate P* ligands. The structure of 3 a was assessed by a combination of X‐ray and NMR spectroscopic studies, which indicate that it is the configuration of the binaphthol moiety (and not that of the dangling benzyl N groups) that determines the configuration of the complex. The effect of the relative configuration of the P* ligand on its iridium(I) coordination chemistry is discussed in the context of our preliminary catalytic results and of apparently random results obtained by other groups in the iridium(I)‐catalyzed asymmetric allylic alkylation of allylic acetates and in rhodium(I)‐catalyzed asymmetric cycloaddition reactions. Further studies with the unlike ligand (aS,R,R)‐(1,1′‐binaphthalene)‐2,2′‐diyl bis{[1‐(1‐naphthalene‐1‐yl)ethyl]phosphoramidite} ( 1 b ) showed a yet different coordination mode, that is, the η4‐arene–metal interaction in (aS,R,R)‐[Ir(cod)(1,2,3,4‐η‐ 1 b ,κP)]+ ( 3 b ). 相似文献
843.
Giuseppe Faita 《Tetrahedron》2010,66(16):3024-5854
The asymmetric Friedel-Crafts reaction between methyl (E)-2-oxo-4-aryl-3-butenoates (1a-c) and activated benzenes (2a-d) has been efficiently catalyzed by the ScIII triflate complex of (4′S,5′S)-2,6-bis[4′-(triisopropylsilyl) oxymethyl-5′-phenyl-1′,3′-oxazolin-2′-yl]pyridine (pybox 3). The 4,4-diaryl-2-oxo-butyric acid methyl esters (4) are usually formed in good yields and the enantioselectivity is up to 99% ee. The sense of the stereoinduction can be rationalized with the same octahedral complex (10) between 1, pybox 3 and Sc triflate already proposed for other reactions involving pyruvates, and catalyzed by the same complex. 相似文献
844.
Dalva E. C. Ferreira Wagner B. De Almeida Ademir Neves Willian R. Rocha 《International journal of quantum chemistry》2010,110(5):1048-1055
Density functional theory (DFT) calculations with different exchange‐correlation functionals were performed for a mixed valence Fe(II)/Fe(III) binuclear complex with μ‐methoxo and two μ‐carboxylate bridging ligands, (1) with geometry optimizations being performed for all possible spin multiplicities (MS = 2, 4, 6, 8, and 10). Within the exchange‐correlation functionals studied, only the hybrid GGA functionals B3P and B3LYP and also the pure GGA functional RPBE, predicts the geometry with high spin (S = 9/2) to be more stable than the geometry with low spin state (S = 1/2) by 20 kcal/mol, in agreement with the experimental findings. These functionals also predict the same stability order for the different spin states, being MS = 10>8>6>2>4. The meta‐GGA functionals TPSS and TPSSh and also the pure GGA functionals BLYP and BP86 predict different stability orders. The computed average EPR g‐tensor, gav, of 2.03, at the B3LYP level, is in good agreement with the experimental findings. Heisenberg exchange coupling constants, J, were calculated within the broken‐symmetry formalism, at the B3LYP level, showing that the two iron centers are antiferromagnetic coupling, with a very weak coupling constant of about ?7 cm?1, in good agreement with the experimental value. Additionally, the effect of using different multiplicities of the reference geometries on the computed J value is discussed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
845.
Jing-An Zhang Mei Pan Rui Yang Zhi-Gang She Wolfgang Kaim Zhi-Jin Fan Cheng-Yong Su 《Polyhedron》2010
The semirigid tridentate 8-(2-pyridinylmethylthio)quinoline ligand (Q1) is shown to form the structurally characterized transition metal complexes [Cu(Q1)Cl2] (1), [Co(Q1)(NO3)2] (2), [Cd(Q1)(NO3)2] (3), [Cd(Q1)I2] (4). [Cu(Q1)2](BF4)2·(H2O)2 (5), [Cu(Q1)2](ClO4)2·(CH3COCH3)2 (6), [Zn(Q1)2](ClO4)2(H2O)2 (7), [Cd2(Q1)2Br4] (8), [Ag2(Q1)2(ClO4)2] (9), and [Ag2(Q1)2(NO3)2] (10). Four types of structures have been observed: ML-type in complexes 1–4, in which the anions Cl−, NO3− or I− also participate in the coordination; ML2− type in complexes 5–7 without direct coordination of the anions BF4− or ClO4− and with more (Cu2+) or less (Zn2+) distorted bis-fac coordinated Q1; M2L2-type in complex 8, in which two Br− ions act as bridges between two metal ions; and M2(μ-L)2-type in complexes 9 and 10, in which the ligand bridges two anion binding and Ag–Ag bonded ions. Depending on electron configuration and size, different coordination patterns are observed with the bonds from the metal ions to Npyridyl longer or shorter than those to Nquinoline. Typically Q1 acts as a facially coordinating tridentate chelate ligand except for the compounds 9 and 10 with low-coordinate silver(I). Except for 6 and 8, the complexes exhibit distinct constraining effects against both G(+) and G(-) bacteria. Complexes 1, 3, 4, 5, 7 have considerable antifungal activities and complexes 1, 5, 7, and 10 show selective effects to restrain certain botanic bacteria. Electrochemical studies show quasi-reversible reduction behavior for the copper(II) complexes 1, 5 and 6. 相似文献
846.
The novel tridentate chiral ligand 2,6-bis{[(1R,2S,4R)-2-hydroxy-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl]}pyridine (1) was readily prepared by reaction of 2,6-dilithiopyridine with (R)-(−)-fenchone. Reaction of 1 with [MoO2(acac)2] resulted in the formation of the new metal-oxo five-coordinated complex [MoO2(ONO)] (2) [ONO = (1 – 2H)]. The reactivity of 2 has been studied and the derivatives [MoS2(ONO)] (3) and [MoO(O2)(ONO)] (4) were prepared. The compounds 1–4 have been characterised by 1H and 13C{1H} NMR, microanalysis and IR spectroscopy. Furthermore, the molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The behaviour of 2 as catalyst in oxotransfer and in nucleophilic substitution of propargylic alcohols reactions has been tested. 相似文献
847.
A series of N^N^N tridentate chromium complexes (C1–C6) bearing 2-(1H-2-benzimidazolyl)-6-(1-(arylimino)ethyl)pyridine derivatives was synthesized and characterized by elemental and spectroscopic analysis along with single-crystal X-ray crystallography. X-ray crystallographic analyses reveal chromium complex C1 as a distorted six-coordinated octahedral geometry. On treatment with modified methylaluminoxane (MMAO), the chromium complexes exhibited high activities for ethylene oligomerization (up to 1.50 × 106 g mol−1 (Cr) h−1) and polymerization (up to 2.06 × 106 g mol−1 (Cr) h−1) at 10 atm ethylene pressure. Various reaction parameters were investigated in detail, and less steric hindrance and electron-withdrawing substituents of ligands enhance the catalytic activities of their chromium complexes. 相似文献
848.
Synthesis and characterization of the dinuclear ruthenium coordination complexes with heteroleptic ligand sets, [Cl(terpy)Ru(tpphz)Ru(terpy)Cl](PF6)2(7) and [(phen)2Ru(tpphz)Ru(terpy)Cl](PF6)3(8), are reported. Both structures contain a tetrapyrido[3,2-α:2′,3′-c:3′′,2′′-h:2′′,3′′-j]phenazine (tpphz) (6) ligand bridging the two metal centers. Complex 7 was obtained via ligand exchange between, RuCl2(terpy)DMSO (5) and a tpphz bridge. Complex 8 was obtained via ligand exchange between, [Ru(phen)2tpphz](PF6)2(4) and RuCl2(terpy)DMSO (5). Metal-to-ligand-charge-transfer (MLCT) absorptions are sensitive to ligand set composition and are significantly red-shifted due to more electron donating ligands. Complexes 7–9 have been characterized by analytical, spectroscopic (IR, NMR, and UV–Vis), and mass spectrometric techniques. The electronic spectral properties of 7, 8, and [(phen)2Ru(tpphz)Ru(phen)2](PF6)4(9), a previously reported +4 analog, are presented together. The different terminal ligands of 7, 8, and 9 shift the energy of the MLCT and the π–π* transition of the bridging ligand. These shifts in the spectra are discussed in the context of density functional theory (DFT). A model is proposed suggesting that low-lying orbitals of the bridging ligand accept electron density from the metal center which can facilitate electron transfer to nanoparticles like single walled carbon nanotubes and colloidal gold. 相似文献
849.
850.
Kinsuk Das Tarak Nath Mandal Somnath Roy Samik Gupta Anil Kumar Barik Partha Mitra Arnold L. Rheingold Susanta Kumar Kar 《Polyhedron》2010
The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO3.H2O](NO3) (1) [Zn(L)2](ClO4)2·2DMF (2) and [Cd(L)(I)2] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized. 相似文献