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本文首次利用铜粉和过氧化苯甲酰的氧化加成反应,在喹啉存在下合成了新的双核铜配合物[Cu2(C6H5COO)4(C9H7N)2]·2H2O.配合物进行了元素分析、摩尔电导、热重分析、红外光谱、电化学等测试;并经X-射线单晶结构分析;确定了配合物的结构.配合物属正交晶系,空间群Pbca,a=19.879(2)A,b=16.982(5)A,c=11.600(4)A,α=β=γ=90°,V=3916A3,Z=4,D=1.475g·cm(-3),R=0.02599,Rw=0.02885. 相似文献
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辅酶B12模型化合物的研究(Ⅵ):轴向及平面配体对RCo(sale… 总被引:2,自引:0,他引:2
合成与表征了两类14种烷基钴Sclriff碱配合物RCo(chel)L(R=CH3,C2H5,n-C3H7,n-C4H9,i-C4H9;chel=salen,SB,L=Py,γ-pic,PPh3),其中RCo(SB)L是一类新的辅酶B12模型化合物,五配位的C2H5Co(SB)也是首次报道,研究了在固态和溶液中配合物的性质,并讨论了影响配合物中Co-C键稳定性的因素。 相似文献
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在不同条件下合成了[Co(phen)mXp]Y1·nH2O型配合物,(m=1,2;p=1,2;1=1-3;n=0-4;phen=邻菲绕啉;X=Cl-,H2O,酒石酸(tart),甘氨酸(gly),α-皮可林酸(pic).DL-两氨酸(ala),L-亮氨酸(leu),L-脯氨酸(pro);Y=Cl-,]并进行了元素分析,热重分析,电子光谱,红外光谱和磁化率测定,计算它们的10Dq和B值.X-ray单晶衍射实验证明:[Co(Phen)2(H2O)2](NO3)3·2H2O,[Co(Phen)2(gly)]Cl2·4H2O均为顺式结构.[Co(Phen)(ala)2]Cl·3H2O,[Co(Phen)(pro)2]ClO4·4/3H2O均为trans(N)结构.在[Co(phen)2X2](n+)型配合物中,X反位的键长均长于顺位键长,其反位效应的顺序为:Cl->羧基,NH2>H2O。 相似文献
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一经式异构体[Co(N-(3-Aminopropyl)-1,3-propanediamine)(1,2-diamino-2-methylpropane)Cl][ ZnCl4]·2H2O的合成及晶体结构 总被引:4,自引:1,他引:4
用过氧化物法合成了新体系「Co(3,3-tri)(ibn)Cl」「ZnCl4」(3,3-tri=N-(3-Aminopropyl)-1,3-propanedia-mine;ibn=1,2-diamino-2-methylpropane)kr g x aa naj sq wsg 「Co(3,3tri)(ibn)Cl」「ZnCl4」.2H2O,解析了其晶体结构。晶体学参数:三斜晶系,空间群P1(#2 相似文献
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《中国化学快报》1994,(10)
THEREACTIONOF(μ_3-CPh)Co_3(CO)_9WITH TRANSITIONMETALCARBONYLANIONM(CO)_3(RCOCp)ANDCHARACTERIZATIONOFCLUSTERS(μ_3-CPh)CO_2M(CO)_8(RCOCPp)(M=Mo,W;R=H,CH_3.C_2H_5O)Authortowhomcormspondenceshouldaddressed.ExperimentalsectionGeneralprocedureandmaterialAlloperationwascarriedoutunderhighlypurenitrogenatmosphereusingshadardSchlenlcandvacuumtechniques.He-cane,benzeneandtetrahydrofuranwerepredriedoversodiumwireanddistilledfromsodium-benzophenoneundernitrogen.NaM(CO)3(RCOCP)andPhCCo3(CO),werepreparedaccordingtoliteratUre 相似文献
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合成了三种以2-溴代对苯二甲酸根为桥联配体的新型双核钴(Ⅱ)的配合物,即[Co2(BTP)(phen)4](ClO4)2·H2O(配合物1)、[Co2(BTP)(Nphen)4](ClO4)2·2H2O(配合物2)和[Co2(BTP)(Bpy)4](ClO4)2·2H2O(配合物3)(BTP=2-溴代对苯二甲酸根,phen=1,10-菲罗啉,Nphen=5-硝基-1,10-菲罗啉,Bpy=2,2′-联吡啶)。使用元素分析、IR、UV-Vis光谱和电导测定方法对该配合物进行了表征。测定了配合物的变温磁化率,并对所得数据进行了理论分析,求得了配合物1、配合物2和配合物3的自旋磁交换积分分别为:2J=-6.5cm-1,2J=-7.8cm-1和2J=-8.9cm-1。对该三配合物进行了体外抗人白血病癌细胞的实验。发现该三配合物均具有一定的抑制癌细胞的活性 相似文献
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Under single-collision beam-gas scattering conditions the reactions Ba+ C_2H, Br、n-C_3H_7Br、1, 2-C_2H_4Br_2、1,3-C_3H_6Br_2 have been studied using laser induced fluore-scence to detect the BaBr X~2∑~+ product. The vibrational distributions, the fractions of the available energy going into vibrational and rotational energy of the BaBr products have been calculated by means. of computer simulation. It has been found that the average vibrationel energies of the BaBr products can be described as a linear function of the mass factors for the reactions Ba+CH_3Br、C_2H_5Br、n-C_3H_7Br、1,3-C_3H_6Br, and that the potential energy surfaces for these reactions are similar. For the reactions Ba+CH_3Br、C_2H_5Br、n-C_3H_7Br, the vibrational increae, but for the reactions Ba+CH_2Br_2、1,2-C_2H_4Br_2、1,3-C_3H_6Br_2, the vibrational excitations of the BaBr products decrease greatly when the number of the carbons increase. 相似文献
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Studies on the photofragmentation of n-C_3H_7I and i-C_3H_7I have been carried out by a photofragment spectrometer with rotatable pulsed molecular beam crossed with KrF excimer laser beam. TOF spectra of the iodine atom fragments (Fig.1, 2) which show the separation of the primary photodissociation channels n-C_3H_7I→n-C_3H_7+I~*(~2P_(1/2)) n-C_3H_7+I(~2p_(3/2)) i-C_3H_7I→i-C_3H_7+I~*(~2P_(1/2)) i-C_3H_7+I(~2P_(3/2)) are obtatned at 12 different angles. The distribution of total translational energy E_(CM) of recoiling photofragments are then determined. The ratios I~*/I of the photodissociation channels of n-C_3H_7I and i-C_3H_7I are measured to be 1.61 and 0.96 respectively (Table 1). The ratios I~*/I obtained by photofragment translational energy measurement in this Lab~[3]. are good in agreement with most of results abtained by IR emission~[5] and LIF~[4] measurement except the data of i-C_3H_7I, which is much different from I~*/I=0.35 reported by Bershon~[4] using LIF method.The extent of internal alkyl fragment excitation E_(int)~R is also determined (Table 2) by energy balance. The fraction of the available energy (E_(av1)=E_(CM)+E_(int)~R) which goes into internal exciatation of the alkyl fragment increases from 12.5% for I~* channe of CH_3I to 64% for both channels of i-C_3H_7I. The results are consistent with direct impulsive dynamic model of unimolecular decomposition based on “soft” alkyl radicals.The facts that the ratio I~*/I decreases with increasing carbon atoms and that the difference of the internal excitation of alkyl radicals between the I~* (~2P_(1/2)) and I (~2P_(3/2)) channelsincreases with increasing carbon atoms should be related and important for better understanding the origin of the I(~2P_(3/2)) channel caused by the potential energy surface crossing~[3]. The results of the internal excitation of the alkyl radicals in the photodissociation are also valuable for prediction of secondary products during the UV photolysis of those alkyl iodides in the gas cell. 相似文献
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KrF激光诱导BrC2F4Br+C2H4反应 总被引:1,自引:1,他引:0
激光诱导化学合成是一有兴趣的课题。不久前已报导了红外激光诱导调聚反应的结果。由于红外激光的加热特性,在许多情况下导致选择性与量子产率的矛盾。因紫外光反应的低温特性,有可能获得较高的选择性。但普通光源是宽带光源,对一个以平方断链为主的链反应,过强的吸收不利于链长的提高,而弱吸收又使反应速度太慢。为此,激光光源是满足最佳吸收的合宜光源。在使用了昂贵的激光光源后,经济上的合理性主要取决于链长 相似文献
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光电子能谱的理论研究已成为量子化学工作者感兴趣的课题,其首要任务是垂直电离势(VIP)的精确计算。根据Koopmans定理,可由分子轨道能得到VIP。然而Koopmans理论是一种粗略的近似,(N-1)-电子体系中分子轨道的调整和N-电子体系与(N-1)-电子体系不等的相关能使Koopmans VIP值存在着两类误差。VIP的E_(△SCF)方法计算虽然考虑了轨道调整这一因素,但需要对N-电子体系和(N-1)-电子体系进行两次SCF计算。理论上讲,E_(ACI)计算能给出正确结果,但计算费用十分昂贵。 相似文献
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(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体属单斜晶系,P2_1空间群.晶胞参数为α=12.140(3),b=13.794(3),c=8.944(3)(?),β=111.68(3)°,V=1391.8(7)(?)~3,Z=2,μ=21.93cm~(-1),D_c=1.43g/cm~3,F(000)=610,Mr=598.0。结构经Patterson函数和Fourier技术解出并经最小二乘修正,最终的偏离因子R为0.046.配合物具有双层夹心结构.其中Sm~(3+)和Na~+通过η~8-环辛四烯基连接。 相似文献
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用Fe_3(CO)_(12)与亚磷酸三硫代苯酯P(SC_6H_5)_3反应得到标题化合物。P(SC_6H_5)_3以其裂解分子片SC_6H_5和P(SC_6H_5)_2配位。用X-ray衍射技术测定了该化合物的晶体结构, 晶体属正交晶系, 空间群为Pbca, a=1.7422(7), b=1.0634(6), c=2.898(12) nm; V=5.370 nm, z=8, D_c=1.579 g·cm~(-3)。由直接法和差值Fourier合成解出全部非氢原子坐标, 并用全矩阵最小二乘法修正, 最后偏离因子R=0.054, R_w=0.058, 分子结构中心的Fe_2SP折叠环沿S…P线或沿Fe—Fe键折叠的二面角(分别为76.1°和82°)比其它具有中心Fe_2S_2, Fe_2P_2和Fe_2SP折叠环的类似化合物中的相应值小, Fe—Fe键长为0.2572 nm, Fe—S(1)—Fe=68.6°, Fe—P—Fe=70.7°。 相似文献
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The cluster (C_6H_5CO_2CH_2C)_2Co_2(CO)_6 has been synthesized and characterized by element analysis, IR, ~1H NMR etc. Its crystal structure has been determined by X-ray diffraction analysis with R=0.060. The crystal is triclinic, space group P_1 with a=0.8933(3) nm, b=1.1830(6) nm, c=1.3199(3) nm, α=65.64(3)°, β=84.55(3)°, γ=72.03(4)°, z=2, D_x=1.584 g cm~(-1) The C≡C and Co-Co form a tetrahedron with appoximate C_(2V) symmetry. The Co-Co bond is metl singal bond. The hybrid state of carbon atoms in the acetylene is between sp and sp~2. 相似文献
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标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。 相似文献
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二DMF-μ-四酞酰替对甲苯胺合二铜的晶体结构和电子结构的研究 总被引:1,自引:0,他引:1
本文报导了的晶体结构。晶体属三斜晶系, 空间群P_1, 晶胞参数: a=1.0761(2), b=1.3930(4), c=1.5117(4) nm; α=114.74(2)°,β=101.82(2)°,γ=95.85(2)°; Z=1。标题化合物为四羧基桥的双核铜(II)簇合物, DMF占据端基位置。Cu-Cu距离0.2635(2) nm, 有微弱成键作用。SCC-EHMO计算表明前线轨道38A_g, 37B_u, 21A_u和20B_g能级相当接近, 化合物为顺磁性, μ(eff)=1.82B.M., 根据顺磁谱出现的由三组峰组成的一套谱, 其中在低场的一组峰分裂7条超精细结构峰, 判断化合物顺磁性应是占据38A_g, 和37B_u分子轨道上未配对电子的贡献。Cu-Cu的成键和反键的σ, π和δ型轨道都填满电子, 因此对成键不起作用。Cu-Cu之间的微弱成键作用, 主要是通过铜与羧基桥原子形成的非定域键的34B_u和18A_u分子轨道的贡献。 相似文献