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1.
Low‐valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square‐planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH2CH2P(tBu)2)2) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)]+. The OsIV complex shows ambiphilic nitride reactivity with SiMe3Br and PMe3, respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4(HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low‐valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions.  相似文献   

2.
A series of hetero-dinuclear CuII-ZnII complexes, [CuZnCl2L1] (1), [CuZnCl2L2] (2), [CuZnBr2L3] (3), [CuZnBr2L4(DMF)] (4), [CuZnCl2L4] (5), [CuZnCl2L5] (6), [CuZnCl2L3] (7) and [CuZnBr2L1] (8), where L1, L2, L3, L4 and L5 are the deprotonated forms of N,N′-bis(3-ethoxysalicylidene)-1,3-propanediamine (H2L1), N,N′-bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine (H2L2), N,N′-bis(3-methoxysalicylidene)-1,3-propanediamine (H2L3), N,N′-bis(salicylidene)-1,3-propanediamine (H2L4) and N,N′-bis(salicylidene)-1,4-butanediamine (H2L5), respectively, have been synthesized and characterized by physico-chemical methods and single-crystal X-ray diffraction. The complexes were tested for their urease inhibitory activity. Complexes 1 and 8 show effective urease inhibitory activity with IC50 values of 2.2 and 10.7 μM. The molecular docking study of the complexes with the Helicobacter pylori urease was performed.  相似文献   

3.
《印度化学会志》2021,98(2):100006
The new cis-dioxomolybdenum (VI) complexes [MoO2(L2)(H2O)] (2) and [MoO2(L3)(H2O)] (3) containing the tridentate hydrazone-based ligands (H2L2 = N'-(3,5-di-tert-butyl-2-hydroxybenzylidene)-4-methylbenzohydrazide and H2L3 = N'-(2-hydroxybenzylidene)-2-(hydroxyimino)propanehydrazide) have been synthesized and characterized via IR, 1H and 13C NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction analysis. The catalytic activities of complexes 2 and 3, and the analogous known complex [MoO2(L1)(H2O)] (1) (H2L1 = N'-(2-hydroxybenzylidene)-4-methylbenzohydrazide) have been evaluated for various oxidation reactions, viz. oxygen atom transfer from dimethyl sulfoxide to triphenylphosphine, sulfoxidation of methyl-p-tolylsulfide or epoxidation of different alkenes using tert-butyl hydroperoxide as terminal oxidant. The catalytic activities were found to be comparable for all three complexes, but complexes 1 and 3 showed better catalytic performances than complex 2, which contains a more sterically demanding ligand than the other two complexes.  相似文献   

4.
A pair of Mo(VI) complexes, [MoO2L1(MeOH)] (1) and [MoO2L2(MeOH)] (2), where L1 and L2 are the dianions of 2-amino-N’-(3-bromo-5-chloro-2-hydroxybenzylidene)benzohydrazide (H2L1) and 2-amino-N’-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (H2L2), respectively, have been prepared and characterized by physico-chemical methods and single-crystal X-ray diffraction. The Mo atom in each complex is coordinated by the phenolate oxygen, imino nitrogen and enolate oxygen of the hydrazone ligand, together with a methanol ligand and two oxo groups, giving a distorted octahedral geometry. The complexes proved to be effective catalysts for the oxidation of various olefins.  相似文献   

5.
Two mononuclear Cu(II) complexes, [Cu(L1H2)](ClO4)1.25Cl0.75·1.25H2O (1) and [Cu(L2H2)](ClO4)2 (2), of the pyridoxal Schiff base ligands N,N′-dipyridoxylethylenediimine (L1H2) and N,N′-dipyridoxyl-1,3-propanediimine (L2H2) are reported. X-ray crystal structures of both complexes are also reported. In both complexes the pyridoxal nitrogen atoms remain protonated. In the solid state, the tetradentate Schiff base ligand is virtually planar in 1, while in 2 the ligand conformation is like an inverted umbrella. In cyclic voltammetry experiments it is found that in these complexes the Cu(III) and Cu(I) states are more easily accessible than in their salen type analogs. The pyridoxal Schiff base complexes are also found to be resistant to oxidative electro-polymerization, unlike their corresponding salicyl aldehyde Schiff base complexes.  相似文献   

6.
Syntheses, characterizations, electrochemistry and catalytic properties for styrene epoxidation of three manganese(III) compounds [MnIIIL1(H2O)(MeOH)](ClO4) (1) [MnIIIL1(N3)(H2O)]·dmf (2) [MnIIIL1(Cl)(H2O)] (3) derived from the Schiff base compartmental ligand N,N′-o-phenylenebis(3-ethoxysalicylaldimine) (H2L1) are reported. The three compounds are characterized by elemental analyses, IR, mass and UV–Vis spectra and conductance values. Single crystal X-ray structures of 1 and 2 have been determined. The structures of 1 and 2 show that these are mononuclear compounds having a salen type structure. In both structures, a dinuclear species is formed by bifurcated hydrogen bonding involving coordinated water molecule. The coordination of chloride in 3 is shown by conductance measurements. The compounds have also been characterized by UV–Vis and mass spectroscopic studies. Cyclic voltammetric and square wave voltammetric studies of the three compounds reveal that these undergo Mn(III)/Mn(II) reduction reversibly with the order of the ease of reduction as 3 > 2 > 1. This order has been explained proposing the composition of active species in solution. Catalytic properties for epoxidation of styrene by all the three complexes using PhIO and NaOCl as oxidant have been studied. The order of both the styrene conversion and styrene epoxidation using the three title compounds is 3 > 1 > 2. Again, it has been observed that more efficient conversion and epoxidation take place when PhIO is used as oxidant.  相似文献   

7.
Novel optical ligands bis(menthane) (H2L1), pinano-para-menthane (H2L2), and carano-para-menthane (H2L3) propylenediaminodioximes are obtained. Diamagentic Co(III) complexes of the composition Co(HL1)Cl2 (I), Co(HL2)Cl2 (II), Co(HL3)Cl2 (III), and Co(HL4)Cl2 · H2O(IV) are synthesized by reactions of CoCl2 with H2L1, H2L2, H2L3 and bis(carane) propylenediaminodioxime (H2L4) in ethanol in air. The crystal and molecular structures of compound I is determined by X-ray diffraction analysis. The crystals are monoclinic with the unit cell parameters a = 7.8385(3) Å, b = 11.4074(6) Å, c = 14.9509(6) Å, β = 104.278(2)°, V = 1295.57(10) Å3, Z = 2, ρ(calcd) = 1.367 g/cm3, F(000) = 564, M = 533.41, space group P21. The crystal structure of complex I consists of individual mononuclear molecules. The Co3+ ion coordinates four N atoms of tetradentate cycle-forming anionic ligand and two Cl atoms. The coordination polyhedron of Cl2N4 is a distorted octahedron. The 13C and 1H NMR spectra of the complexes synthesized confirm coordination of four N atoms of a ligand.  相似文献   

8.
The reaction of a series of tripodal ligands, H3L1,2 and L3-6, with [M(PPh3)2Cl2] (M = Ru, Os) affords a family of coordination cage compounds of the type [MIIIL1,2] (1-4) or [MIIL3-6](BPh4)2 (5-12). The Schiff base ligands (H3L1, L3, L5) have been synthesized by condensation of tris(2-aminoethyl)amine with salicylaldehyde, pyridine-2-aldehyde and 1-methyl-2-imidazolecarboxaldehyde. These ligands were further reduced and subsequently methylated to form the new ligands (H3L2, L4, L6). Single crystal X-ray diffraction studies of 1 and 2 show that the tripodal ligand wraps around the metal center as a hexadentate ligand to form a cage. All the synthesized compounds have been thoroughly characterized by ESI-MS, FT-IR, UV-Vis and NMR spectroscopic methods. To the best of our knowledge, this is the first ever report of osmium complexes with tris(2-aminoethyl)amine based tripodal ligands. DFT calculations were performed to obtain geometry optimized structures of all the other complexes (3-12).  相似文献   

9.
The bi-functional carbamoyl methyl pyrazole ligands, C5H7N2CH2CONBu2 (L1), C5H7N2CH2CONiBu2 (L2), C3H3N2CH2CONBu2 (L3), C3H3N2CH2CONiBu2 (L4) and C5H7N2CH2CON(C8H17)2 (L5) were synthesized and characterized by spectroscopic and elemental analysis methods. The selected coordination chemistry of L1 to L4 with [UO2(NO3)2 · 6H2O], [La(NO3)3 · 6H2O] and [Ce(NO3)3 · 6H2O] has been evaluated. Structures for the compounds [UO2(NO3)2 C5H7N2CH2CONBu2] (6) [UO2(NO3)2 C5H7N2CH2CONiBu2] (7) and [Ce(NO3)3{C3H3N2CH2CONiBu2}2] (11) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of the ligand L5 with U(VI) and Pu(IV) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) up to 10 M HNO3 but not for Am(III). Thermal studies of the compounds 6 and 7 in air revealed that the ligands can be destroyed completely on incineration.  相似文献   

10.
Two new N-pyrazole, P-phosphinite hybrid ligands 3-(3,5-dimethyl-1H-pyrazol-1-yl)propyldiphenylphosphinite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L4) are presented. The reactivity of these ligands and two other ligands reported in the literature (3,5-dimethyl-1H-pyrazol-1-yl)methyldiphenylphosphinite (L1) and 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L2) towards [RhCl(CO)2]2 (1) have been studied and complexes [RhCl(CO)L] (L = L2 (2), L3 (3) and L4 (4)) have been obtained. For L1 only decomposition products have been achieved. All complexes were fully characterised by analytical and spectroscopic methods and the resolution of the crystalline structure of complexes 2 and 3 by single-crystal X-ray diffraction are also presented. In these complexes, the ligands are coordinated via κ2(N,P) to Rh(I), forming metallocycles of seven (2 and 4) or eight (3) members and finish its coordination with a carbonyl monoxide and a trans-chlorine to phosphorus atom. In both complexes, weak intermolecular interactions are present. NMR studies of complexes 2-4 show the chain N-(CH2)x-O becomes rigid and the protons diastereotopic.  相似文献   

11.
Four molybdenum(VI) thiosemicarbazonato complexes have been synthesized and characterized. The dinuclear complexes [(MoO2L1)2] (1) and [(MoO2L2)2] (3) have been prepared by the reaction of [MoO2(acac)2] with 2-hydroxyacetophenone N(4)-cyclohexyl (H2L1) and N(4)-phenyl (H2L2) thiosemicarbazones in alcoholic medium. Mononuclear dioxomolybdenum(VI) complexes of the type [MoO2L1py] (2) and [MoO2L2py] (4) have been prepared by the reaction of 1 or 3 with pyridine (py) in alcoholic medium. In all the complexes, molybdenum is coordinated by two terminal oxo-oxygen atoms, (Ot), oxygen, nitrogen and sulfur atoms from the principal ligand and by an oxygen atom from the second unit in 1, and by a nitrogen atom from pyridine in complexes 2 and 4. All complexes have been spectroscopically characterized. The molecular structures of complexes 1, 2 and 4 have been determined by the single crystal X-ray diffraction method.  相似文献   

12.
The synthesis, characterization, spectroscopic and electrochemical properties of trans-[CoIII(L1)(Py)2]ClO4 (I) and trans-[CoIII(L2)(Py)2]ClO4 (II) complexes, where H2L1 = N,N′-bis(5-chloro-2-hydroxybenzylidene)-1,3-propylenediamine and H2L2 = N,N′-bis(5-bromo-2-hydroxybenzylidene)-1,3-propylenediamine, have been investigated. Both complexes have been characterized by elemental analysis, FT-IR, UV-Vis, and 1H NMR spectroscopy. The crystal structure of I has been determined by X-ray diffraction. The coordination geometry around cobalt(III) ion is best described as a distorted octahedron. The electrochemical studies of these complexes revealed that the first reduction process corresponding to Co(III/II) is electrochemically irreversible accompanied by dissociation of the axial Co-N(Py) bonds. The in vitro antimicrobial activity of the Schiff bse ligands and their corrsponding complexes have been tested against human pathogenic bacterias such as Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, and Escherichia coli. The cobalt(III) complexes showed lower antimicrobial activity than the free Schiff base ligands.  相似文献   

13.
Two new oxidovanadium(V) complexes, [VO(L1)(L)] (I) and [VO(L2)(L)] (II), where L1 and L2 are the dianionic form of N'-(2-hydroxy-5-methoxybenzylidene)pivalohydrazide (H2L1) and N'-(2-hydroxy-3-methoxybenzylidene)pivalohydrazide (H2L2), respectively, and L is the monoanionic form of 8-hydroxyquinoline (HL), were prepared and characterized by elemental analysis, infrared and electronic spectra, and 1H NMR spectra. Structures of the complexes were further confirmed by single crystal X-ray determination (CIF files CCDC nos. 1477854 (I), 1477856 (II)). H2L1 and H2L2 coordinate to the V atoms through the phenolate O, imino N, and enolate O atoms. 8-Hydroxyquinoline coordinates to the V atoms through bidentate ON donor set. The V atoms of the complexes are in octahedral coordination with the oxo group furnished the octahedral geometry. The complexes show effective antibacterial activity against Bacillus subtilis.  相似文献   

14.
Reaction of bis(amide) sodium Na2[(1R,2R)-(−)-1,2-(NSiMe3)2-C6H10] (Na2[L1]) with Ti(OiPr)2Cl2 in different conditions gave mixed-ligand complexes [Ti(OiPr)Cl][L1] (1) or [Ti(OiPr)2Cl]2[L1] (2); 2 is a dinuclear titanium example in which Ti atoms are bridged by nitrogen and oxygen atoms simultaneously forming a distorted rhombic core. Reaction of the amine-amidinate ligand (1R,2R)-(−)-1-Li[NC(Ph)N(SiMe3)]-2-(NHSiMe3)-C6H10(Li[L2]) or rarely linked bis(amidinate) ligand Li2[(1R,2R)-(−)-1,2-{NC(Ph)N(SiMe3)}2-C6H10](Li2[L3]) with ZrCl4 yielded the unbridged and bridged bis(amidinate) complexes ZrCl2[L2]2 (3) and [ZrCl2(THF)][L3] (4), respectively; Moreover, the reaction of (1R,2R)-(−)-1-Li[NC(Ph)N(SiMe3)]-2-Li(NSiMe3)C6H10(Li2[L2]) with Ti(OiPr)2Cl2 gave a new type of tridentate amido-amidinate product [Ti(OiPr)2][L2] (6), which is a distinct model compared to [Ti(OiPr)2Cl][L2] (5) yielded from Li[L2]. All the products have been characterized by X-ray crystallography and the structural studies are presented detailedly comparing with relevant compounds.  相似文献   

15.
A series of dioxomolybdenum(VI) complexes with similar hydrazone ligands have been prepared, specifically [MoO2L1(MeOH)] (1), [MoO2L2(MeOH)] (2) and [MoO2L3(MeOH)] (3), where L1, L2 and L3 are the dianionic forms of 2-chloro-N′-(2-hydroxybenzylidene)benzohydrazide, 2-chloro-N′-(2-hydroxy-5-methylbenzylidene)benzohydrazide and N′-(3-bromo-5-chloro-2-hydroxybenzylidene)-2-chlorobenzohydrazide, respectively. The complexes were characterized by physicochemical and spectroscopic methods and also by single-crystal X-ray determination. The hydrazone ligands coordinate to the Mo atoms through their phenolate O, imine N and enolic O atoms. The Mo atoms are six-coordinated in octahedral geometries. The complexes show high catalytic activities and selectivities in the epoxidation of cyclohexene with tert-butylhydroperoxide as primary oxidant.  相似文献   

16.
Charge density studies of chemical bonds for two iron complexes, [(NO)Fe(S,S-C6H4)2] [PPN] (1), where PPN = N(Pph3)2 and Fe3(NO)3(S,S-C6H4)3 (2) are investigated in terms of the topological properties at bond critical points based on the ‘atoms in molecule’ theory. The one electron reduction form (1R) of complex 1 and the one electron oxidation form (2O) of complex 2 are also included for comparison. The X-ray absorption spectroscopy of Fe K- and LIII,II-edges, as well as the N/S K-edge are applied to verify the illustration in the variation of the electronic structures. Based on the ρc, ?2ρc, and Hb values among the compound studied, Fe-S/N can be regarded as polarized covalent bond, and Fe-N bonds show stronger covalent character than that of the Fe–S bond, which is believed to be a highly polarized covalent bond.  相似文献   

17.
Unique thiocyanate-connected 1-dimensional chain Cu(II) coordination polymer (CP), namely, [Cu2L1(μ1,3-SCN) (η1SCN)]n (1), was produced in the existence of KSCN and Cu(NO3)2·3H2O utilizing an underlying multisite N,O donor Schiff base ligand (L1H2). [N,N′-bis(3-methoxysalicylidenimino)-1,3-daminopropane] (L1H2), the Schiff base ligand is a 1:2 M ratio condensation product of 1,3-diaminopropane and O-vaniline in the methanol medium. The as-created CP 1 has been investigated with various characterization approaches like powder X-ray diffraction (PXRD), fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), -thermogravimetric analysis (TGA) and single crystal X-ray diffraction (SCXRD) analyses. And the mechanism and therapeutic effect of this CP on sepsis was discussed and its specific mechanism was also assessed. First of all, for the infected animals, their survival rate was recorded after the bacterial infection and treatment of complex. Besides this, utilizing the enzyme linked immunosorbent assay (ELISA) assay, the inflammatory cytokines levels that released into plasma were determined after the exposure of compound.  相似文献   

18.
《印度化学会志》2021,98(4):100049
The new azo-imine ligands 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl)diazenyl) phenylimino)methyl)phenol, H2L1, 1a, and 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl) diazenyl)p-chlorophenylimino)phenol, H2L2, 1b, were prepared. Reaction of H2L1;1a, and H2L2;1b, with uranyl nitrate hexahydrate afforded the mononuclear complexes of compositions [U(O)2(L1)(H2O)]; 2a, and [U(O)2(L2)(H2O)]; 2b, complexes respectively. The newly synthesised ligands (1a and 1b) and the complexes (2a and 2b) were characterised unequivocally. The x-ray structure of 2a was determined. The tetradentate dianionic ligand (L1)2- coordinated the uranium ion equatorially with a water molecule in the same plane. Two axially coordinated oxo ligands completed the overall pentagonal bipyramid geometry around U(VI) ion. Structural pattern, electron transfer properties (oxidation near 1.32 ​V vs Ag/AgCl) and electronic transitions of [U(O)2(L1)(H2O)]; 2a, and [U(O)2(L2)(H2O)]; 2b have been rationalized by DFT calculations.  相似文献   

19.
《印度化学会志》2021,98(12):100250
Within this work, two novel Cu(II) and Mn(II)-based coordination polymers (CPs) along with chemical compositions of {[Cu2(L1)(1,4-NDC)2]·3H2O}n (1, 1,4-H2NDC = Naphthalene-1,4-dicarboxylic acid, L1 ​= ​di(1H-imidazole-1-yl)methane) and [Mn3(L2)2(H2O)2(1,4-NDC)2]n (2, L2 ​= ​1,4-di(1H-imidazole-1-yl)benzene) have been completed in success via related metal salts reaction with 1,4-H2NDC ligand in existence of various N-donor co-ligands. We discovered its application values on the surgical site infections (SSI) along with corresponding mechanism in the interim. We evaluated inflammatory cytokines released into the urine through ELISA detection kit after compound treatment. Then, we discovered the inhibitory effect of compound on the bacterial biofilm formation via real time RT-PCR.  相似文献   

20.
The diamagnetic complexes [Pd2(H2L1)Cl4] (I), [Pd2(H2L2)Cl4] (II), and Pd2(H2L3)Cl4(III) with chiral ligands derived from the natural monoterpenoid (R)-(+)-limonene are obtained (H2 L1 is ethylenediamine dioxime, H2L2 is piperazine dioxime, and H2L3 is propylenediamine dioxime). According to X-ray diffraction data, the crystal structures of complexes I and II are composed of binuclear acentric molecules. The coordination polyhedra PdN2Cl2 are trapeziums (squares distorted in a tetrahedral manner) made up of two N atoms of the tetradentate bridging cyclic ligands H2L1 and H2L2 and two Cl atoms. The fragments PdCl2 are trans in the complexes. The 13C and 1H NMR spectra of complexes I and II in CDCl3 also suggest their binuclear structures.  相似文献   

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