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1.
The Ir–NHC complex 6 was successfully synthesized from the reaction of axially chiral binaphthyl dibenzimidazolium salt 5 with [Ir(COD)Cl]2 (COD = 1,5‐cyclooctadiene) in tetrahydrofuran in the presence of KOtBu base under reflux. Its unique crystal structure is unambiguously disclosed by X‐ray diffraction. Complex 6 is orthorhombic, with space group P212121, unit cell dimensions a = 12.1406(16) Å, b = 19.110(3) Å, c = 20.312(3) Å, α = β = γ = 90° and volume 4712.6(11) Å3, Z = 4, Dcalc = 1.930 Mg m?3. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
2.
Two new cobalt complexes were successfully synthesized from the reaction of binaphthyl Schiff base 2 with Co(OAc)2 in the presence of sodium methoxide at 80 °C for 24 h and Co(acac)3 in toluene under reflux. Their unique crystal structures are unambiguously disclosed by X‐ray analysis. Complex 3 is triclinic, space group P1 , unit cell dimensions a = 10.742(2) Å, b = 11.153(2) Å, c = 12.715 Å, α = 79.865(3) °, β = 76.053 °, γ = 72.532(4) °, volume 1401.3(5) Å3, Z = 2. Complex 4 is triclinic, space group P1 , unit cell dimensions a = 10.801(2) Å, b = 12.554(3) Å, c = 15.219(3) Å, α = 105.672(4) °, β = 103.048 °, γ = 104.594(4) °, volume 1824.8(7) Å3, Z = 2, calculated density 1.428 Mg m−3. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
3.
Sandeep P. Netalkar Priya P. Netalkar Anupama A. Nevrekar Vidyanand K. Revankar 《应用有机金属化学》2016,30(4):170-180
The reaction of [PdCl2(CH3CN)2] and N(4)‐substituted phenylaminoacetohydrazone ligands (LH) in methanol at room temperature afforded air‐ and moisture‐stable palladium(II) complexes of two types with general formulae [Pd(LH)Cl] and [Pd2(LH)(L)]Cl. An unusual coordination mode of ligand LH is observed, in which the ligand coordinates through N(4)H nitrogen and without enolization of the carbonyl group of the hydrazone moiety in both mono‐ and bimetallic complexes. The crystal structure of the complexes reveals that the oxime LH reacts with [PdCl2(CH3CN)2] presumably via the elimination of HCl from hydrazine NH. All the synthesized Pd(II) complexes were evaluated as catalysts in the Suzuki cross‐coupling reaction of aryl halides, activated 4‐bromoacetophenone and non‐activated bromobenzene, with phenylboronic acid in aqueous medium. In both cases, i.e. with activated and non‐activated aryl halides, all the complexes show moderate conversion leading to biaryls with yields in the range 50–65%. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
4.
Chiral allylic secondary alcohols have been resolved efficiently by catalytic hydrogenation with ruthenium complexes derived from the new chiral atropisomeric (R)‐ and (S)‐BITIANP. These catalytic sistems have been applied to the resolution of NCS‐382, a selective antagonist of the γ‐hydroxybutyric acid (GHB) receptors. NCS‐382 may play a role as a central neuromodulator and possesses several neuropharmacological properties that can be investigated in detail only if both eutomer and distomer are available in bulk. Copyright © 2000 John Wiley & Sons, Ltd. 相似文献
5.
The oxidative kinetic resolution of various racemic secondary alcohols with PhI(OAc)(2) catalyzed by chiral [Mn(III)(salen)] complexes in the presence of KBr was studied in a water/organic solvent mixture. The dramatic, synergetic effect of additives, organic solvent, and the substituents of chiral salen ligands on the enantioselectivities of the reactions is reported. Results from UV/Vis spectroscopy and ESI-MS studies provide evidence that these reactions are induced by the formation of a high-valent manganese intermediate. 相似文献
6.
Some new asymmetric 1,1 ′‐disubstituted ferrocene‐derived Schiff‐bases have been prepared and used as ligands in the preparation of their Co(II), Cu(II), Ni(II) and Zn(II) metal chelates. These synthesized ligands and their metal chelates have been characterized by their physical, analytical and spectral data. These have also been used for screening against pathogenic bacterial species, e.g. Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Klebsiella pneumonae and have been found to be a novel class of organometallic‐based antibacterials. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
7.
In this work, four bimetallic Ru(II)–Ir(III) complexes with the general formula [(bpy)2Ru(bpm)Ir(C^N)2](PF6)3 (bpy = 2,2‐bipyridine, bpm = 2,2′‐bipyrimidine, C^N = 2‐phenylpyridinato ( 2 ), (2‐p‐tolyl)pyridinato ( 3 ), 2‐(2,4‐difluorophenyl)pyridinato ( 4 ), and 2‐thienylpyridinato ( 5 )) were synthesized. Complexes 2 – 5 were characterized by NMR spectroscopy, high‐resolution mass spectrometry, and elemental analysis. The structures of the complexes 2 and 4 were further confirmed by single‐crystal X‐ray diffraction analysis. All the complexes display strong absorption in the high‐energy UV region assigned to intraligand (IL) transitions, and the lower energy bands are ascribed to metal‐to‐ligand charge transfer (MLCT) transitions. The reduction and oxidation behavior of the complexes 2 – 5 were examined by cyclic voltammetry. Variation of the ligands on Ir(III) center resulted in significant changes in electrochemical properties. 相似文献
8.
A stable dimeric mono‐coordinated NHC–Pd(II) complex with bridging iodine atoms was synthesized and characterized by single‐crystal X‐ray diffraction. It has been successfully applied to the Suzuki–Miyaura cross‐coupling reaction under aerobic conditions. Good to excellent yields were obtained in most cases with the addition of H2O. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
9.
(PhCH2NH2)2CuCl2 ( 2 ), an effective oxidation reagent for oxidative coupling of 2‐naphthylamine ( 1 ) to form 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ), is studied. Oxidative coupling of 2‐naphthylamine ( 1 ) is carried out at room temperature in methanol by (PhCH2NH2)2CuCl2 ( 2 ), which is prepared from CuCl2·2H2O and benzylamine in methanol, to give a novel copper complex, [{1,1′‐(C10H6)2‐2,2′‐(NH2)2}2CuCl]Cl·CH3OH·3H2O ( 3 ), in good yield. Treatment of 3 with aqueous HCl (37%), followed by addition of NH3·H2O (25%), gives 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ) in a moderate yield (total yield from 1 : > 70%). Both 2 and 3 have been characterized by various techniques, such as infrared spectroscopy, elemental analyses and X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
10.
Shuxiang Wang Wenhao Chu Yuechai Wang Siyuan Liu Jinchao Zhang Shenghui Li Haiying Wei Guoqiang Zhou Xinying Qin 《应用有机金属化学》2013,27(7):373-379
Eight novel Pt(II), Pd(II), Cu(II) and Zn(II) complexes with 4’‐substituted terpyridine were synthesized and characterized by elemental analysis, UV, IR, NMR, electron paramagnetic resonance, high‐resolution mass spectrometry and molar conductivity measurements. The cytotoxicity of these complexes against HL‐60, BGC‐823, KB and Bel‐7402 cell lines was evaluated by MTT assay. All the complexes displayed cytotoxicity with low IC50 values (<20 μm ) and showed selectivity. Complexes 3 , 5 , 7 and 8 exerted 9‐, 5‐, 12‐ and 7‐fold higher cytotoxicity than cisplatin against Bel‐7402 cell line. The cytotoxicity of complexes 3 , 5 , 6 , 7 and 8 was higher than that of cisplatin against BGC‐823 cell line. Complexes 3 , 7 and 8 showed similar cytotoxicity to cisplatin against KB cell line. Complex 7 exhibited higher cytotoxicity than cisplatin against HL‐60 cell line. Among these complexes, complex 7 demonstrated the highest in vitro cytotoxicity, with IC50 values of 1.62, 3.59, 2.28 and 0.63 μm against HL‐60, BGC‐823, Bel‐7402 and KB cells lines, respectively. The results suggest that the cytotoxicity of these complexes is related to the nature of the terminal group of the ligand, the metal center and the leaving groups. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
11.
NHC‐Pd complex based on 1,3‐bis (4‐ethoxycarbonylphenyl) imidazolium chloride: synthesis,structure and catalytic activity in the synthesis of axially chiral benzophenone hydrazone
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Wenzeng Duan Zhaofeng Sun Yanmin Huo Yanke Liu Guangqing Wu Ruifeng Wang Shuang Wu Qingxia Yao Shuwen Gong 《应用有机金属化学》2018,32(9)
A novel NHC–Pd complex of 1,3‐bis (4‐ethoxycarbonylphenyl) imidazolium chloride has been synthesized and characterized by 1H NMR, 13C NMR, IR and X‐ray single‐crystal diffraction studies. TG analysis shows that the NHC‐Pd complex is stable under 208 °C. The catalytic activities have been explored for the synthesis of axially chiral N‐(2′‐methoxy‐1,1′‐binaphthalen‐2‐yl) benzophenone hydrazone. The result indicates that the novel NHC‐Pd complex can achieve better catalytic activity than the Pd‐phosphine catalysts in the synthesis of axially chiral N‐(2′‐methoxy‐1,1′‐binaphthalen‐2‐yl) benzophenone hydrazone. 相似文献
12.
Novel 4,4′‐dichloro‐2,2′‐[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L) and its complexes [CuL] and {[CoL(THF)]2(OAc)2Co} have been synthesized and characterized by elemental analyses, IR, 1H‐NMR and X‐ray crystallography. [CuL] forms a mononuclear structure which may be stabilized by the intermolecular contacts between copper atom (Cu) and oxygen atom (O3) to form a head‐to‐tail dimer. In {[CoL(THF)]2(OAc)2Co}, two acetates coordinate to three cobalt ions through Co? O? C? O? Co bridges and four µ‐phenoxo oxygen atoms from two [CoL(THF)] units also coordinate to cobalt ions. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
13.
Some 1,1′‐(dicarbohydrazono) ferrocenes have been prepared by condensing 1,1′‐diacetylferrocene with either 2‐furoic hydrazide, 2‐thiophenecarboxylic hydrazide or 2‐salicylic hydrazide. All the ligands synthesized were characterized by IR and NMR spectroscopy and elemental analysis data (carbon, hydrogen, nitrogen) and then were used as ligands to react with cobalt(II), copper(II), nickel(II) and zinc(II) metals as chlorides to afford metal complexes having the general formula M(L)Cl2. IR and electronic spectral data, magnetic moment and elemental analyses were used in the structural investigation of the metal complexes synthesized. The ligands synthesized and their metal(II) complexes have been screened for their in vitro antibacterial activity against Escherichia coli, Klebsiella pneumoniae, Proteus mirabilis, Pseudomonas aeruginosa, Salmonella typhi, Shigella dysenteriae, Bacillus cereus, Corynebacterium diphtheriae, Staphylococcus aureus and Streptococcus pyogenes bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata. The results of these studies show the metal complexes to be more antibacterial and antifungal than the uncomplexed ligands. However, the potency of all the ligands synthesized and their metal complexes was lower than that of the standard drugs. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
14.
Kateryna E. Gubina Oleg A. Maslov Elizaveta A. Trush Victor A. Trush Vladimir A. Ovchynnikov Svetlana V. Shishkina Vladimir M. Amirkhanov 《Polyhedron》2009,28(13):2661-2666
This paper presents examples of mixed-ligand Co(II), Cu(II), Ni(II) and Mn(II) complexes, with a distorted octahedral coordination geometry, with 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands. The complexes of the general type ML2·Lig (where M = Co(II), Cu(II), Ni(II), Mn(II); L− = {Cl3C(O)NP(O)R2}− (R = NHBz, NHCH2CHCH2, NEt2); Lig = 2,2′-dipyridyl or 1,10-phenanthroline) were synthesised and characterised by means of X-ray diffraction, IR and UV–Vis spectroscopy. The phosphortriamide ligands are coordinated via oxygen atoms of phosphoryl and carbonyl groups involved in six-membered metal cycles. The additional ligands 2,2′-dipyridyl or 1,10-phenanthroline are coordinated to the central atom, forming five-membered cycles. 相似文献
15.
E. Chinnaraja R. Arunachalam Manoj K. Choudhary R. I. Kureshy P. S. Subramanian 《应用有机金属化学》2016,30(2):95-101
Enantiopure macrocyclic ligands were synthesized from (1R,2R)‐(+)‐ and (1S,2S)‐(?)‐diphenylethylenediamine with 3,3'‐methylenebis(5‐(tert‐butyl)‐2‐hydroxybenzaldehyde) and characterized. The chirality transfer and chiral inversion from ligand to copper(II) metal centre were studied using circular dichroism spectroscopy. The enantiopure binuclear copper(II) complexes (ΔΔ and ΛΛ) were used as catalysts for asymmetric nitroaldol reaction to generate β‐nitroalcohol with 88% yield and 67% enantioselectivity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
16.
K. J. Tony J. Rajaram V. Mahadevan C. S. Swamy 《Reaction Kinetics and Catalysis Letters》1997,60(1):145-155
RuX2(DMSO)4 (X=Cl,cis; Br,trans) undergoes ligand substitution in N,N-dimethylformamide (DMF) to give RuX2(DMSO)3DMF, which catalyzes the oxidation of secondary alcohols by NMO to ketones. Kinetics of the reaction catalyzed bytrans-RuBr2(DMSO)4 differed from that ofcis-RuCl2(DMSO)4. A mechanism is proposed involving the formation of Ru(IV)oxo species as the active intermediate and a rate expression is
derived. 相似文献
17.
Gema Marcelo Raquel de Francisco María Jos Gonzlez-lvarez Francisco Mendicuti 《Journal of photochemistry and photobiology. A, Chemistry》2008,200(2-3):114-125
Steady-state and time-resolved fluorescence techniques were used to study (R)- and (S)-[1,1′-binaphthalene]-2,2′-diol (1,1′-binaphthol or BINOL) dilute solutions of different polarity solvents, as well as their inclusion complexes with α- and βcyclodextrins (CDs) in water. BINOLs in dilute water solutions exhibited a surprisingly high fluorescence anisotropy that was explained as being due to the formation of fairly large order π–π stacking aggregates in aqueous polar media. Stoichiometries, formation constants and the changes of enthalpy and entropy upon inclusion were also obtained by measuring the variation of the fluorescence intensity with [CD] and temperature. Results agree with the formation of 1:1 stoichiometry complexes, but the association constants are rather low and very similar for both enantiomers. Molecular mechanic calculations in the presence of water were employed to study the formation of BINOL complexes with both α- and βCDs. For the most stable structures of any of the complexes only a small portion of the guests, in agreement with thermodynamics parameters and quenching experiments, penetrates inside the CD cavities. Driving forces for 1:1 inclusion processes may be dominated by non-bonded van der Waals host:guest interactions. The low guest:host binding constants and poor enantioselectivity of α- and βCDs for BINOLS may be a consequence of the BINOL aggregation in water. 相似文献
18.
Benzimidazole‐based silver(I)–N‐heterocyclic carbene complexes as anti‐bacterials: synthesis,crystal structures and nucleic acids interaction studies
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Patrick O. Asekunowo Rosenani A. Haque Mohd. R. Razali Srinivasa Budagumpi 《应用有机金属化学》2015,29(3):126-137
A series of new benzimidazolium salts as N‐heterocyclic carbene (NHC) precursors has been synthesized. Reactions of these salts with Ag2O with varying metal‐to‐salt ratio facilitate the formation of a series of new binuclear and mononuclear Ag(I)–NHC complexes. All compounds were characterized using physicochemical and spectroscopic techniques. Single‐crystal X‐ray diffraction study reveals a binuclear structure for one of the complexes and a mononuclear one for two others. These complexes exist as cationic Ag(I)–NHC complexes with the chelation of carbene carbons to the silver centre in an almost linear manner. The compounds were screened for their anti‐bacterial activities against Staphylococcus aureus (ATCC 12600) as a Gram‐positive bacterium and Escherichia coli (ATCC 25922) as a Gram‐negative bacterium. The results show that both bacteria appear markedly inhibited. Furthermore, the results suggest the possibility of steric variation as a modulation of the anti‐bacterial activities. The nuclease activities of the compounds were assessed using gel electrophoresis and the results indicate that these complexes can cleave or degrade DNA and RNA via a non‐oxidative mechanism. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
19.
Chiral nickel(II) and palladium(II) catalysts bearing strong electron‐withdrawing fluorine groups: synthesis,characterization and their application in catalytic polymerization for ethylene and styrene
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Jianchao Yuan Jie Zhao Fengying Song Weibing Xu Yanqiong Mu Jingjing Chen Zhenghua Zhang 《应用有机金属化学》2014,28(7):484-494
A series of new chiral and achiral nickel(II) and palladium(II) complexes, {bis[N,N′‐(2,6‐diethyl‐4‐naphthylphenyl)imino]‐1,2‐dimethylethane}dibromonickel 3a , {bis[N,N′‐(4‐fluoro‐2‐methyl‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel rac‐(RS)‐ 3b , {bis[N,N′‐(4‐fluoro‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel rac‐(RR/SS)‐ 3c and {bis[N,N′‐(4‐fluoro‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dichloropalladium rac‐(RR/SS)‐ 3d were successfully synthesized and characterized. The molecular structures of representative ligand rac‐(RS)‐ 2b , nickel complex 3a , rac‐(RR/SS)‐ 3c and palladium complex rac‐(RR/SS)‐ 3d were determined by X‐ray crystallography. The structures of complexes 3a and rac‐(RR/SS)‐ 3c have pseudo‐tetrahedral geometry about the nickel center, showing C2 molecular symmetry. However, the structure of palladium complex rac‐(RR/SS)‐ 3d has pseudo‐square planar geometry about the palladium center, showing C2 molecular symmetry. Complex 3e {bis[N,N′‐(2,6‐dimethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel was also synthesized for comparison. Nickel complex rac‐(RS)‐ 3b bearing strong electron‐withdrawing fluorine group in the para‐aryl position and a chiral sec‐phenethyl group in the ortho‐aryl position of the ligand (one methyl group in the ortho‐aryl position) displays the highest catalytic activity for ethylene and styrene polymerization, and produced highly branched polyethylene and syndiotactic‐rich polystyrene. However, palladium complex rac‐(RR/SS)‐ 3d shows low catalytic activity for ethylene and styrene polymerization due to the poor leaving group, Cl, attached to palladium and the unfavorable molecular structure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
20.
A series of bimetallic chiral [Co(salen)]‐type complexes were successfully applied for the synthesis of optically pure β‐blockers via phenolic kinetic resolution (PKR) of racemic epichlorohydrin [2‐(chloromethyl)oxirane; ( ± )ECH]. The reaction proceeded readily at room temperature and consequently provided enantiomerically enriched corresponding α‐aryloxy alcohols with excellent enantioselectivities of up to 98% ee. The PKR method described in this work is highly efficient and straightforward strategy for the synthesis of chiral building blocks. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献