主(脱铝Y分子筛纳米腔)-客(Co,Mn和Co_x/Mn_x三核金属簇合物)纳米复合物催化剂高效催化环己烯环氧化反应（英文）

采用模板合成法制备了在脱铝Y分子筛纳米腔中含有Co,Mn,和Co/Mn混合物的三核金属簇合物的复合物催化剂,包括[Mn3(O)(CH3COO)6-(py)3]-Y,[Co3(O)(CH3COO)6-(py)3],[Co2Mn(O)(CH3COO)6-(py)3]-Y和[CoM n2(O)(CH3COO)6-(py)3]-Y],并运用傅里叶变换红外光谱、紫外-可见光光谱、前场扫描电镜、X射线衍射和原子吸收光谱对其进行了表征.包裹的金属簇合物在环己烯环氧化反应中表现出较高的催化活性,反应以H2O2/O2为氧化剂,在加热机械搅拌下进行,所得环氧化物产率在82.5%-90.7%.在该催化体系中,Na Br用作氧化助剂可以提高反应性能.在所制多相催化体系中,含单核的金属簇合物催化活性更高,其中以Mn3(O)-DAZY化合物的效率最高.各催化剂活性顺序为Mn3(O)-DAZY?Co3(O)-DAZY?Mn2Co(O)-DAZY?MnC o2(O)-DAZY.     

纳米二氧化钛催化苯乙烯环氧化反应的研究

通过烯烃的环氧化反应 ,可制得活泼的有机合成中间体——环氧化物 ,再通过选择性开环或功能团转化 ,可以方便地合成多种有价值的化合物 .因此 ,催化烯烃环氧化的反应得到广泛的研究 ,其中含钛催化剂具有较好的催化性能 ,如 Ti- ZSM- 5沸石 [1,2 ] 、Ti- ZSM- 1 1沸石[3 ,4 ] 在 H2 O2 存在下就有高的催化活性 ;α-和β- [Si W9Ti3 O4 0 ]10 -也有一定的催化活性 [5] ;Sharpless等人 [6]采用 Ti[OCH( CH3 ) 2 ]4和酒石酸二乙酯诱导体 ,可高选择性催化烯丙醇的不对称环氧化反应 .纳米 Ti O2 ,由于颗粒小 ,处于固体表面的原子多 ,表…     

新型含2,5-二-（3,5-二甲基吡唑-4-巯基）-1,3,4-噻二唑-M(M=Co2+,Cd2+,Mn2+)配合物的合成、晶体结构及其抑菌活性研究

将配体L[2,5-二-(3,5-二甲基吡唑-4-巯基)-1,3,4-噻二唑]与Co(NO3)2 6H2O,Cd(NO3)2 4H2O和MnCl2 4H2O进行配位反应,得到三个配合物[Co(L)2(H2O)4](NO3)2 4(CH3CH2OH)(1),[Cd(L)2(H2O)4](NO3)2 4(CH3CH2OH)(2),[Mn(L)2(Cl)2(CH3OH)2]2(CH3OH)(3),并用元素分析,FT-IR和X射线单晶衍射进行了表征.分析结果表明,配体L呈"U"形,配合物1～3呈"S"形.配合物中Co(II),Cd(II),Mn(II)的配位环境均为扭曲八面体,每个金属离子同时和两个配体进行配位.配体和配合物体外抑菌活性研究结果表明,配体及其配合物都有一定的抑菌活性.     

非对称Schiff碱过渡金属配合物模拟酶催化烯烃环氧化(Ⅰ)

研究了温和条件下以亚碘酰苯为氧源,非对称性的和对称性的Mn(Ⅲ)Schiff碱配合物[Mn(Ⅲ)(CBP－phen－Xsal)Cl,X=H,Cl,Br,NO₂,CH₃,OCH₃]和[Mn(Ⅲ)(CBP－R－CBP)Y,R=CH₂CH₂－,－CH(CH₃)CH₂－,－C₆H₄－;Y=Cl,OCH₃]催化非官能性烯烃苯乙烯、环己烯和α-甲基苯乙烯的环氧化反应.结果表明,非对称配合物Mn(Ⅲ)(CBP－phen－Xsal)Cl是一个良好的催化非官能性烯烃环氧化反应的催化剂体系;中心金属离子Mn(Ⅲ)的电子结合能越小,催化环氧化效果越好;对上述3种烯烃环氧化物最好收率分别达到73％、100％和92％.     

两个由2,3,5-吡啶三酸构筑的三维网状配位聚合物的合成、晶体结构和性质研究

2,3,5-吡啶三酸在水热条件下分别与Mn(CH3COO)2·4H2O和Co(CH3COO)2·4H2O反应,得到了2种金属有机骨架(MOFs)配合物[Mn1.5(2,3,5-pta)(H2O)4]n(1)和[Co1.5(2,3,5-pta)(H2O)4]n(2),其中2,3,5-H3pta=2,3,5-吡啶三酸。利用元素分析、红外、热重和X-射线单晶衍射分析进行了表征。分析结果表明2个配合物属于同构晶体:晶系为单斜,空间群为P21/c,其中,吡啶三酸配体完全脱去3个质子,并分别与4个六配位的金属离子相连,在空间形成一种三维网络状结构。热重分析表明,配合物1的稳定性要高于配合物2。     

Y型分子筛固载Co(Salprn)配合物的制备及催化烯烃环氧化性能

采用自由配体法将双水杨醛缩丙二胺席夫碱钴配合物Co(Salprn)封装于Y型分子筛超笼中,并通过X射线衍射、漫反射UV-Vis光谱、FT-IR光谱和差热分析技术对所制备的催化剂进行了表征。该催化剂样品( [Co(Salprn)]-Y)在苯乙烯环氧化反应中较纯配合物Co(Salprn)表现出很高的催化活性。反应条件（包括溶剂、催化剂用量、异丁醛浓度和反应时间）对催化性能有较大影响。研究结果还表明,[Co(Salprn)]-Y对其他烯烃的环氧化也具有较高催化活性。其活性顺序为苯乙烯﹥环己烯﹥环辛烯﹥正辛烯。     

缺位类型磷钨酸盐催化的烯烃环氧化反应

主要合成了两种杂多磷钨酸盐环氧化催化剂,分别是由单缺位Keggin类型磷钨酸阴离子或者饱和结构的磷钨酸阴离子与十六烷基三甲基季铵盐阳离子构成,即[n-C16H33N(CH3)3]4Na3PW11O39(PW11)以及[n-C16H33N(CH3)3]3PW12O40(PW12),将其与低毒性的乙酸乙酯、30%的双氧水、烯烃构成催化环氧化反应体系,以环辛烯的环氧化反应为模型反应,着重探讨了PW11与PW12的催化性能产生明显差异的原因,并通过傅里叶变换-红外光谱,核磁共振谱以及催化剂溶解性实验给出了合理的解释.首先,在进行环辛烯的环氧化反应的动力学研究中,我们发现相同的反应条件下,PW11的催化活性明显高于PW12的催化活性,当反应进行至10min,以PW11为催化剂的反应体系,环辛烯的转化率已达到89%,而相应的采用PW12为催化剂的反应体系,环辛烯的转化率仅仅为11%.通过核磁磷谱(31PNMR)表征证明:当PW11和PW12与双氧水反应10min时PW11已降解产生大量的活性物种,而PW12的31PNMR谱并没有显示降解产物的谱峰.溶解性实验则更近一步说明,两个催化剂在双氧水的作用下均可降解形成小分子的物...     

利用碳氢键活化合成钴的钳式配合物及其性质研究（英文）

利用CoMe(PMe3)4或者CoMe3(PMe3)3与[PCP]-钳式配体,[Ph2P(ortho-C6H4)]2CH2(1),室温下反应,在实现碳氢键活化的同时,合成了钴的钳式配合物[PCP]Co(I)(PMe3)(2).配合物2与卤代烃C6Cl6,EtBr,n-BuBr以及CH3I反应,分别生成了单电子氧化加成产物3~5,[PCP]Co(II)X(PMe3)[X=Cl(3),Br(4),I(5)].X射线衍射分析测定了配合物2~6的结构.     

双功能金属卟啉催化环氧化合物与 CO2 偶联反应合成环碳酸酯

 合成了新颖的双功能水溶性金属卟啉 催化剂 M(TTMAPP)I4(X) (M = Co, Fe, Mn 和 Cr; X = OAc, CF3COO, CCl3COO, OTs, Cl, Br 和 I), 研究了它们催化 CO2 与末端环氧化合物合成环碳酸酯的偶联反应. 分别考察了反应温度、不同金属的 Lewis 酸中心、抗衡离子和催化剂重复使用次数对反应性能的影响. 当以 Co(III)(TTMAPP)I4(OAc) 为催化剂, 底物与催化剂摩尔比为 1 000, 温度为 353 K, CO2 压力为 667 kPa 和无溶剂条件下, 反应 5 h 时丙烯环碳酸酯收率为 95.4%. 在 298 K, 底物与催化剂之比为 2 000 时, 加入 1 ml 甲醇, 反应 24 h 丙烯环碳酸酯收率为 19.4%. 催化剂可以用乙醚回收, 循环使用 5 次后催化剂活性没有明显降低.     

混合价四核锰配合物[Mn4O2（ClCH2COO）7（bipy）2]·H2O的合成、晶体结构及性质研究

在乙腈溶液中,由混合价三核锰配合物[Mn3O(ClCH2COO)6(py)2]?(H2O)(py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn3IIIMnII)四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]?H2O.采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构.标题化合物晶体属于三斜晶系,空间群P-1,晶胞参数:a=0.89854(13)nm,b=1.4027(2)nm,c=1.9037(3)nm,α=93.518(3)°,β=96.736(3)°,γ=94.875(3)°,V=2.3680(6)nm3,Z=2,Dc=1.734g/cm3,F(000)=1238,GOF=1.036,R1=0.0592,wR2=0.1162[I>2σ(I)].在标题化合物中,配位结构单元中心为一蝶型[Mn4(μ3-O)2]7+多核簇,含有2个Mn3(μ3-O)单元,具有近似C2对称轴.4个Mn离子均为六配位,外围配体为7个氯乙酸根和2个2,2′-联吡啶,处于变形的八面体环境.变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用,但在低温下的磁相互作用较为复杂.     

Highly luminescent gold(I)-silver(I) and gold(I)-copper(I) chalcogenide clusters

The reactions of [AuClL] with Ag(2)O, where L represents the heterofunctional ligands PPh(2)py and PPh(2)CH(2)CH(2)py, give the trigoldoxonium complexes [O(AuL)(3)]BF(4). Treatment of these compounds with thio- or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)(3)]BF(4) (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)(4)]PF(6) to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh(2)py)(3)]BF(4) with silver or copper salts give [E(AuPPh(2)py)(3)M](2+) (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au(3)Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh(2)py)(3)](+) units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh(2)CH(2)CH(2)py)(3)]BF(4) with silver and copper salts give complexes with [E(AuPPh(2)CH(2)CH(2)py)(3)M](2+) stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of AuM interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.     

Synthesis, structure, and catalytic properties of V(IV), Mn(III), Mo(VI), and U(VI) complexes containing bidentate (N, O) oxazine and oxazoline ligands

Synthesis of seven complexes containing oxazoline ([(L(1))(2)V=O] (4), [(L(1))(2)MoO(2)] (5), [(L(1))(2)UO(2)] (6); HL(1) (1) [HL(1) = 2-(4',4'-dimethyl-3'-4'-dihydroxazol-2'-yl)phenol]), chiral oxazoline ([(L(2))(2)UO(2)] (7); HL(2) (2) [HL(2) = (4'R)-2-(4'-ethyl-3'4'-dihyroxazol-2'-yl)phenol]), and oxazine ([(L(3))(2)V=O] (8), [(L(3))(2)Mn(CH(3)COO(-))] (9), [(L(3))(2)Co] (10); HL(3) (3) [HL(3) = 2-(5,6-dihydro-4H-1,3-oxazolinyl)phenol]) and their characterization by various techniques such as UV-vis, IR, and EPR spectroscopy, mass spectrometry, cyclic voltammetry, and elemental analysis are reported. The novel oxazine (3) and complexes 4, 5, 8 and 9 were also characterized by X-ray crystallography. Oxazine 3 crystallizes in the monoclinic system with the P2(1)/n space group, complexes 4 and 9 crystallize in the monoclinic system with the P2(1)/c space group, and complexes 5 and 8 crystallize in the orthorhombic system with the C222(1) space group and the P2(1)2(1)2(1) chiral space group, respectively. The representative synthetic procedure involves the reaction of metal acetate or acetylacetonate derivatives with corresponding ligand in ethanol. Addition of Mn(OAc)(2).4H(2)O to an ethanol solution of 3 gave the unexpected complex Mn(L(3))(2).(CH(3)COO(-)) (9) where the acetate group is coordinated with the metal center in a bidentate fashion. The catalytic activity of complexes 4-9 for oxidation of styrene with tert-butyl hydroperoxide was tested. In all cases, benzaldehyde formed exclusively as the oxidation product.     

New coordination polymers with extended arm cyclotriguaiacyclene ligands: 1D chains, and interpenetrating or polycatenating 2D (4(2).6(2))(4.6(2))2 networks

A series of new 1D chain and 2D coordination polymers with cyclotriguaiacylene-type ligands are reported. A zig-zag 1D coordination chain is found in complex [Cd(2)(4ph4py)(NO(3))(3)(H(2)O)(2)(DMA)(2)]·(NO(3))·(DMA)(4), where 4ph4py = tris[4-(4-pyridyl)benzoyl]-cyclotriguaiacylene and DMA = dimethylacetamide, while complex [Zn(4ph4py)(2)(CF(3)COO)(H(2)O)]·(CF(3)COO)(NMP)(7), where NMP = N-methylpyrrolidone, has a doubly bridged coordination chain structure. Complexes [M(3ph3py)(NO(3))(2)]·(NMP)(4) where M = Co or Zn, 3ph3py = tris[3-(3-pyridyl)benzoyl]cyclotriguaiacylene, are isostructural and feature 1D ladder coordination chains. Complexes [Cd(2)(4ph4py)(2)(NO(3))(4)(NMP)]·(NMP)(9)(H(2)O)(4) and [Co(4ph4py)(H(2)O)(2)]·(NO(3))(2)·(DMF)(2), where DMF = dimethylformamide, both have (3,4)-connected 2D coordination polymers with a rare (4(2).6(2))(4.6(2))(2) topology. A 2D coordination polymer with this topology is also found in complex [Co(2)(3ph4py)(2)(NO(3))(H(2)O)(5)]·(NO(3))(3)·(DMF)(9) where 3ph4py = tris[3-(4-pyridyl)benzoyl]cyclotriguaiacylene. All 2D coordination polymer complexes are interpenetrating or polycatenating. [Co(2)(3ph4py)(2)(NO(3))(H(2)O)(5)](3+)polymers form a 2D→3D polycatenation showing self-complementary "hand-shake" interactions between the host-type ligands.     

A family of manganese rods: syntheses, structures, and magnetic properties

The reaction of the mixed-valent metal triangles [Mn(3)O(O(2)CR)(6)(py)(3)] (R = CH(3), Ph, C(CH(3))(3)) with the tripodal ligands H(3)thme (1,1,1-tris(hydroxymethyl)ethane) and H(3)tmp (1,1,1-tris(hydroxymethyl)propane) in MeCN, produces a family of manganese rodlike complexes whose structures are all derived from a series of edge-sharing triangles. Variable temperature direct current (dc) magnetic susceptibility data were collected for all complexes in the 1.8-300 K temperature range in fields up to 7.0 T. Complex 1, [Mn(12)O(4)(OH)(2)(PhCOO)(12)(thme)(4)(py)(2)], has an S = 7 ground state with the parameters g = 1.98 and D = -0.13 K. Complex 2, [Mn(8)O(4)((CH(3))(3)CCO(2))(10)(thme)(2)(py)(2)] has a ground state of S = 6, with g = 1.81 and D = -0.36 K. Complex 3, [Mn(7)O(2)(PhCO(2))(9)(thme)(2)(py)(3)], has a spin ground states of S = 7 with the parameters g = 1.78 and D = -0.20 K. The best fit for complex 4, [Mn(6)((CH(3))(3)CCO(2))(8)(tmp)(2)(py)(2)], gave a spin ground state of S = 3 with the parameters g = 1.73 and D = -0.75 K, but was of poorer quality than that normally obtained. The presence of multiple Mn(2+) ions in the structure of 4 leads to the presence of low-lying excited states with energy levels very close to the ground state, and in the case of complex 5, [Mn(6)(CH(3)CO(2))(6)(thme)(2)(H(2)tea)(2)], no satisfactory fit of the data was obtained. DFT calculations on 4 and 5 indicate complexes with spin ground states of S = 4 and S = 0 respectively, despite their topological similarities. Single-crystal hysteresis loop and relaxation measurements show complex 1 to be a SMM.     

Ligating properties of a potentially tetradentate Schiff base [(CH3)2NCH2CH2N=CHC6H3(OH)(OMe)] with zinc(II), cadmium(II), cobalt(II), cobalt(III) and manganese(III) ions: synthesis and structural studies

A series of Zn(II), Cd(II), Co(II), Co(III) and Mn(III) complexes with the Schiff base [(CH3)2NCH2CH2N=CHC6H3(OH)(OMe)], LH, derived from 2-dimethylaminoethylamine and o-vanillin, has been synthesised and structures of all the products have been established by X-ray crystallography. In the cases of zinc and cadmium, dimeric complexes [Zn(LH)2(NCS)] [Zn2(L)(mu(1,1)-CH3COO)(NCS)3] (1), [Cd2(L)2(Cl)2] (2) and [Cd2(L)2(NCS)2] (3), and for cobalt and manganese, monomeric complexes [Co(LH)2(NCS)]2 [Co(NCS)4] (4), [Co(LH)2(NCS)]ClO4 (5), [Co(L)(N3)(o-vanillinate)] x 0.5 MeOH (6) and [Mn(LH)2(MeOH)2](ClO4)3 (7), are formed with various terminal ligands. All the complexes have been characterised by elemental analysis and IR spectra. UV-Vis and NMR spectroscopy, magnetic, and electrochemical studies, were also carried out where feasible. The Schiff base functions as a bi-, tri- or tetra-dentate chelating agent and coordinates via the protonated or deprotonated phenolic oxygen, amine and imine nitrogens, and only in case of 1 with the methoxy oxygen atoms, to the metal ion leading to the formation of mono- or bi-metallic complexes.     

SYNTHESIS,CRYSTAL STRUCTURES,AND LUMINESCENT PROPERTIES OF Zn(II)/Cd(II) COMPLEXES ASSEMBLED BY 4-AMINOPHENYLHYDROXAMIC ACID

Journal of Structural Chemistry - Two coordination complexes, namely [Zn2(4-APha)2(CH3COO)2(H2O)2] (1) and [Cd(4-APha)(CH3COO) (H2O)0.5]4·6H2O (2)...     

Synthesis, structure, and magnetic properties of three 1D chain complexes based on high-spin metal-cyanide clusters: [Mn(III)6M(III)] (M = Cr, Fe, Co)

On the basis of high-spin metal-cyanide clusters of Mn(III)(6)M(III) (M = Cr, Fe, Co), three one-dimensional (1D) chain complexes, [Mn(salen)](6)[Cr(CN)(6)](2)·6CH(3)OH·H(2)O (1), [Mn(5-CH(3))salen)](6)[Fe(CN)(6)](2)·2CH(3)CN·10H(2)O (2), and [Mn(5-CH(3))salen)](6)[Co(CN)(6)](2)·2CH(3)CN·10H(2)O (3) [salen = N,N'-ethylenebis(salicylideneiminato) dianion], have been synthesized and characterized structurally as well as magnetically. Complexes 2 and 3 are isomorphic but slightly different from complex 1. All three complexes contain a 1D chain structure which is comprised of alternating high-spin metal-cyanide clusters of [Mn(6)M](3+) and a bridging group [M(CN)(6)](3-) in the trans mode. Furthermore, the three complexes all exhibit extended 3D supramolecular networks originating from short intermolecular contacts. Magnetic investigation indicates that the coupling mechanisms are intrachain antiferromagnetic interactions for 1 and ferromagnetic interactions for 2, respectively. Complex 3 is a magnetic dilute system due to the diamagnetic nature of Co(III). Further magnetic investigations show that complexes 1 and 2 are dominated by the 3D antiferromagnetic ordering with T(N) = 7.2 K for 1 and 9.5 K for 2. It is worth noting that the weak frequency-dependent phenomenon of AC susceptibilities was observed in the low-temperature region in both 1 and 2, suggesting the presence of slow magnetic relaxations.     

A comparative XAS and X-ray diffraction study of new binuclear Mn(III) complexes with catalase activity. indirect effect of the counteranion on magnetic properties

Four new binuclear Mn(III) complexes with carboxylate bridges have been synthesized: [[Mn(nn)(H(2)O)](2)(mu-ClCH(2)COO)(2)(mu-O)](ClO(4))(2) with nn = bpy (1) or phen (2) and [[Mn(bpy)(H(2)O)](2)(mu-RCOO)(2)(mu-O)](NO(3))(2) with RCOO = ClCH(2)COO (3) or CH(3)COO (4). The characterization by X-ray diffraction (1 and 3) and X-ray absorption spectroscopy (XAS) (1-4) displays the relevance of this spectroscopy to the elucidation of the structural environment of the manganese ions in this kind of compound. Magnetic susceptibility data show an antiferromagnetic coupling for all the compounds: J = -2.89 cm(-1) (for 1), -8.16 cm(-1) (for 2), -0.68 cm(-1) (for 3), and -2.34 cm(-1) (for 4). Compounds 1 and 3 have the same cation complex [[Mn(bpy)(H(2)O)](2)(mu-ClCH(2)COO)(2)(mu-O)](2+), but, while 1 shows an antiferromagnetic coupling, for 3 the magnetic interaction between Mn(III) ions is very weak. The four compounds show catalase activity, and when the reaction stopped, Mn(II) compounds with different nuclearity could be obtained: binuclear [[Mn(phen)(2)](mu-ClCH(2)COO)(2)](ClO(4))(2), trinuclear [Mn(3)(bpy)(2)(mu-ClCH(2)COO)(6)], or mononuclear complexes without carboxylate. Two Mn(II) compounds without carboxylate have been characterized by X-ray diffraction: [Mn(NO(3))(2)(bpy)(2)][Mn(NO(3))(bpy)(2)(H(2)O)]NO(3) (5) and [Mn(bpy)(3)](ClO(4))(2).0.5 C(6)H(4)-1,2-(COOEt)(2).0.5H(2)O (8).     

Synthesis and characterization of ethylbis(2-pyridylethyl)amineruthenium complexes and two different types of C-H bond cleavage at an ethylene arm

Ruthenium complexes bearing ethylbis(2-pyridylethyl)amine (ebpea), which has flexible -C(2)H(4)- arms between the amine and the pyridyl groups and coordinates to a metal center in facial and meridional modes, have been synthesized and characterized. Three trichloro complexes, fac-[Ru(III)Cl(3)(ebpea)] (fac-[1]), mer-[Ru(III)Cl(3)(ebpea)] (mer-[1]), and mer-[Ru(II)Cl(3){η(2)-N(C(2)H(5))(C(2)H(4)py)═CH-CH(2)py}] (mer-[2]), were synthesized using the Ru blue solution. Formation of mer-[2] proceeded via a C-H activation of the CH(2) group next to the amine nitrogen atom of the ethylene arm. Reduction reactions of fac- and mer-[1] afforded a triacetonitrile complex mer-[Ru(II)(CH(3)CN)(3)(ebpea)](PF(6))(2) (mer-[3](PF(6))(2)). Five nitrosyl complexes fac-[RuX(2)(NO)(ebpea)]PF(6) (X = Cl for fac-[4]PF(6); X = ONO(2) for fac-[5]PF(6)) and mer-[RuXY(NO)(ebpea)]PF(6) (X = Cl, Y = Cl for mer-[4]PF(6); X = Cl, Y = CH(3)O for mer-[6]PF(6); X = Cl, Y = OH for mer-[7]PF(6)) were synthesized and characterized by X-ray crystallography. A reaction of mer-[2] in H(2)O-C(2)H(5)OH at room temperature afforded mer-[1]. Oxidation of C(2)H(5)OH in H(2)O-C(2)H(5)OH and i-C(3)H(7)OH in H(2)O-i-C(3)H(7)OH to acetaldehyde and acetone by mer-[2] under stirring at room temperature occurred with formation of mer-[1]. Alternative C-H activation of the CH(2) group occurred next to the pyridyl group, and formation of a C-N bond between the CH moiety and the nitrosyl ligand afforded a nitroso complex [Ru(II)(N(3))(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([8]) in reactions of nitrosyl complexes with sodium azide in methanol, and reaction of [8] with hydrochloric acid afforded a corresponding chloronitroso complex [Ru(II)Cl(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([9]).     

回火处理对LiNi1/3Co1/3Mn1/3O2结构和电化学性能的影响

以硝酸锂、四水合乙酸镍、四水合乙酸钴、四水合乙酸锰、氨水和草酸为原料,通过共沉淀-燃烧法合成了锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2,采用XRD、SEM和充放电试验对合成产物进行了表征,研究了回火处理对合成产物结构和电化学性能的影响.实验结果表明,嫩烧反应形成的LiNi1/3C1/3Mn31/3O2结...