铜(Ⅱ)与苯基羧酸(HPCA)和2,2''''-联吡啶衍生物(dpx)混配配合物的合成和表征

合成了铜（Ⅱ）与苯基羧酸根［ＰＣＡ－＝苯甲酸根（Ｂｚ－），２－苯乙酸根（ＰＡｃ－），３－苯丙酸根（ＰＰｒ－），４－苯丁酸根［ＰＢｕ－）］和２，２′－联吡啶衍生物（ｄｐｘ：２，２′－联吡啶胺ｄｐａ、２，２′－联吡啶酮ｄｐｋ、２，２′－联吡啶甲烷ｄｐｍ）三大系列１２种新的三元配合物。用元素分析、摩尔电导、红外光谱、１Ｈ核磁共振、差热分析等实验方法表征了它们的组成和性质。确定该系列配合物化学组成为Ｃｕ（ＰＣＡ）２（ｄｐａ）、Ｃｕ（ＰＣＡ）２（ｄｐｍ）、Ｃｕ（ＰＣＡ）２（ｄｐｋ）·ｎＨ２Ｏ（ｎ＝２－４）。它们具有相似的组成和配位方式。它们的可能结构为：二个ＰＣＡ－与Ｃｕ（Ⅱ）单齿配位，一个ｄｐｘ与Ｃｕ（Ⅱ）Ｎ，Ｎ二齿螯合配位。ｄｐｋ的羰基在金属离子Ｃｕ２＋的存在下发生水化作用成ｄｐｋ·Ｈ２Ｏ。用１ＨＮＭＲ法研究了Ｃｕ（Ｂｚ）２（ｄｐｘ）·ｎＨ２Ｏ和Ｃｕ（ＰＡｃ）２（ｄｐｘ）·ｎＨ２Ｏ二个体系其分子内或分子间可能存在的非共价键作用。     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

六方氮化硼与石墨在形成层间化合物上的差异的理论研究

根据量子化学密度泛函B3LYP方法的计算结果,从六方氮化硼(h-BN）与石墨的前线轨道能级和两对离子探针（C^ 和C^-）的作用能所表现出来的在电亲和性上的差异以及金属层间化合物的电子结构,分析了h-BN不能形成金属层间化合物的原因。     

胆甾液晶／聚合物多组分体系的结构与性质研究Ⅳ．ChN／Poly（MMA－co－BMA）混合体系的X－射线衍射研究

用Ｘ－射线衍射法详细研究了ＣｈＮ／Ｐｏｌｙ（ＭＭＡ－ｃｏ－ＢＭＡ）共混体系在胆笛（Ｃｈ）相，近晶（Ｓ）相及结晶（Ｋ）态的分子排列。并给出了将液晶态的分子排列冻结在体系中，从而实现信息存储功能的条件。     

水合希土硝酸盐与本并及单环己基-12-冠-4配合物的合成、性质及晶体结构

在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）。研究了它们的ＩＲ及＾１ＨＮＭＲ性质，并测定了四种单晶的结构，用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ     

1－N－（苯并咪唑－1－乙酰基）－4－苯基－3－氨基硫脲金属配合物的合成及结构表征

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物。所有化合物均经元素分析、ＩＲ、１ＨＮＭＲ和热重分析等表征。红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子、烯醇式硫羰基硫原子以及Ｃ＝Ｎ１和Ｃ＝Ｎ２的氮原子与金属配位     

[Cu2（Gly—GlyO）2（4,4‘—bpy）（OH）2].10H2O配合物的合成,晶 …

合成了以４，４－ｂｐｙ为中继基，Ｇｌｙ，ＧｌｙＯ为螯环的新型双核铜配合物。经Ｘ射线单昌结构分析确定该配合化合物的化学式为「（Ｈ２ＣＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２０Ｃｕ（ＯＨ）－（Ｈ２ＮＣＨ２ＣＯＮＨＨＣＨ２ＯＯ）．」１０Ｈ２Ｏ。     

层状复合氧化La4BaCu5—xMxO13（M=Mn,Co）的物化性质和结构中活性 …

合成了一系列结构为层磁状ＡＢＯ３的复合氧化物Ｌａ４ＢａＣｕ５－ｘＭｘＯ１３（Ｍ＝Ｍｎ，Ｃｏ），并利用ＸＲＤ、Ｘ射线能谱、氧程序升温脱附和化学分析方法对它们的结构和活性氧种进行了研究。ＸＲＤ分析结果表明：它们的结构为五层的ＡＢＯ３结构。玫瑰中ａ４ＢａＣｕ５Ｏ１３中掺Ｍｎ或Ｃｏ之后，样品中明显存在的Ｍ－Ｃｕ（Ｍ＝Ｍｎ，Ｃｏ）之间的协同作用，并且Ｃｏ－Ｍｎ之间协同作用明显比Ｃｕ－Ｃｏ的强。     

1—N—（苯并咪唑—1—乙酰基）—4—苯基—3—氨基硫脲金属配合物的合成及结…

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ），Ｃｏ（Ⅱ），Ｎｉ（Ⅱ），Ｃｕ（Ⅱ），Ｃｄ（Ⅱ），Ｚｎ（Ⅱ），ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物，所有化合物均经元素分析，ＩＲＨＮＭＲ和热重分析等表征，红外光谱表明，配体以四齿方式通过烯醇式羰基氧还子，烯醇式硫羰基硫原子以及Ｃ＝Ｎ＾１和Ｃ＝Ｎ＾２的氮原子与金属配位。     

含硼—氮配键漆酚高分子铜（Ⅱ）：配合物的特性及其表征

含硼－氮配键漆酚高分子与氯化铜的反应产物ＰＵＢＮ－Ｃｕ（Ⅱ）在亚硫酸钠水溶液中能使甲基丙烯酸甲酯于室温下聚合。用红外光谱、Ｘ射线光电子能谱、高效液相色谱等方法对ＰＵＢＮ－Ｃｕ（Ⅱ）进行了表征，并探讨了其引发甲基丙烯酸甲酯聚合的特性和机理。     

吸附O的Cu(110)c(2×1)表面原子结构和电子态

采用第一性原理的密度泛函理论方法计算了清洁Cu(110)表面和吸附O原子的Cu(110) c(2×1)表面的原子结构, 结构弛豫和电子结构, 得到了各种表面结构参数. 分别计算了O原子在Cu(110)表面三个可能吸附位置吸附后的能量, 并给出了能量最低的吸附位置上各层原子的弛豫特性和态密度. 结果表明O吸附后的Cu(110)表面有附加列(added-row)再构的特性, O原子吸附在最表层铜原子上方, 与衬底Cu原子的垂直距离为0.016 nm, 以氧分子为能量基准的吸附能为－1.94 eV; 同时由于Cu 3d- O 2p态的杂化作用使得低于费米能级5.5~6.0 eV的范围内出现了局域的表面态. 计算得到清洁的和氧吸附的Cu(110)表面的功函数分别为4.51 eV和4.68 eV. 电子态密度的结果表明：在Cu(110) c(2×1) 表面O吸附的结构下, 吸附O原子和金属衬底之间的结合主要是由于最表层Cu原子3d态和O原子2p态的相互作用.     

金属铜升温熔化过程的分子动力学模拟

采用分子动力学方法模拟了金属铜的升温熔化过程.原子间作用势采用FS (Finnis-Sinclair)势，结构分析采用双体分布函数(PCF)、均方位移(MSD)等方法.计算结果表明,在连续升温过程中，金属铜在1444 K熔化，在该熔化点的扩散系数为4.31×10－9 m2•s－1.上述结论与实验值相当接近，并且比之采用EAM镶嵌原子势所作模拟得到的结果更佳，说明FS势可以用来处理象液铜这样较复杂的无序体系.本文指出了升温速率在金属熔化过程中所起的作用.     

LnCu2O4(Ln=Gd,Nd)电子结构的XPS研究

用XPS测定了LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到LnCu2O4中稀土金属的3d电子结合能比相应的稀土金属简单氧化物的3d结合能低0.8～0.9 eV,而Cu的2p电子结合能比CuO的高0.4～0.5 eV,因此推断在LnCu2O4的Ln－O－Cu链中存在Cu→O→Ln电荷转移.XPS分析还表明LnCu2O4的Cu原子上有较低的电荷密度,但不存在混合价态.此外,通过比较价电子能谱,发现NdCu2O4的Ln 4f Cu 3d O 2p价带中心比GdCu2O4的价带中心向Fermi能级移近了3.4 eV,而且NdCu2O4的价带谱更窄.     

LnCu_2O_4(Ln=Gd,Nd)电子结构的XPS研究

用 XPS测定了 LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到 LnCu2O4中稀土金属的 3d电子结合能比相应的稀土金属简单氧化物的 3d结合能低 0.8～ 0.9 eV,而 Cu的 2p电子结合能比 CuO的高 0.4～ 0.5 eV,因此推断在 LnCu2O4的 Ln－ O－ Cu链中存在 Cu→ O→ Ln电荷转移 .XPS分析还表明 LnCu2O4的 Cu原子上有较低的电荷密度,但不存在混合价态 .此外,通过比较价电子能谱,发现 NdCu2O4的 Ln 4f Cu 3d O 2p价带中心比 GdCu2O4的价带中心向 Fermi能级移近了 3.4 eV,而且 NdCu2O4的价带谱更窄 .     

No-pair bonding in coinage metal dimers

High-level ab initio calculations at the coupled cluster with single and double substitutions and perturbative treatment of triple substitutions, CCSD(T), level of theory have been carried out for the dimers of coinage metal atoms Cu, Ag, and Au in the ground 1Sigma(g)+ state and in the excited 3Sigma(u)+ state. All of the calculations have been carried out with the inclusion of scalar-relativistic effects via the normalized elimination of the small component (NESC) method. For the dimers in the triplet state, nonzero bond dissociation energies are obtained which vary from 1.3 kcal/mol for 3Cu2 to 4.6 kcal/mol for 3Au2. Taking into account that, in bulky high-spin copper clusters, the bond dissociation energy per atom increases steeply to the value of ca. 19 kcal/mol, the results obtained in the present paper suggest that the bond dissociation energy per atom in high-spin gold clusters may reach extremely high values exceeding 20 kcal/mol thus becoming comparable to the usual bonding due to the spin-pairing mechanism.     

取代基对1-甲基尿嘧啶与N-甲基乙酰胺氢键复合物中氢键强度的影响

使用密度泛函理论B3LYP方法和二阶微扰理论MP2方法对由1-甲基尿嘧啶与N-甲基乙酰胺所形成的氢键复合物中的氢键强度进行了理论研究, 探讨了不同取代基取代氢键受体分子1-甲基尿嘧啶中的氢原子对氢键强度的影响和氢键的协同性. 研究表明: 供电子取代基使N－H…O＝C氢键键长r(H…O)缩短, 氢键强度增强; 吸电子取代基使N－H…O＝C氢键键长r(H…O)伸长, 氢键强度减弱. 自然键轨道(NBO)分析表明: 供电子基团使参与形成氢键的氢原子的正电荷增加, 使氧原子的负电荷增加, 使质子供体和受体分子间的电荷转移量增多; 吸电子基团则相反. 供电子基团使N－H…O＝C氢键中氧原子的孤对电子轨道n(O)对N－H的反键轨道σ^*(N－H)的二阶相互作用稳定化能增强, 吸电子基团使这种二阶相互作用稳定化能减弱. 取代基对与其相近的N－H…O＝C氢键影响更大.     

Comments on the nature of the bonding in oxygenated dinuclear copper enzyme models

The nature of the bonding in model complexes of di-copper metalloenzymes has been analyzed by means of the electronic localization function (ELF) and by the quantum theory of atoms in molecules (QTAIM). The constrained space orbital variations (CSOV) approach has also been used. Density functional theory (DFT) and CASSCF calculations have been carried out on several models of tyrosinase such as the sole Cu2O22+ central core, the Cu2O2(NH3)62+ complex and the Cu2O2(Imidazol)62+ complex. The influence on the central Cu(2)O(2) moiety of both levels of calculation and ligand environment have been discussed. The distinct bonding modes have been characterized for the two major known structures: [Cu(2)(mu-eta(2): eta(2)-O(2))](2+) and [Cu(2)(mu-O(2))](2+). Particular attention has been given to the analysis of the O-O and Cu-O bonds and the nature of the bonding modes has also been analyzed in terms of mesomeric structures. The ELF topological approach shows a significant conservation of the topology between the DFT and CASSCF approaches. Particularly, three-center Cu-O-Cu bonds are observed when the ligands are attached to the central core. At the DFT level, the importance of self interaction effects are emphasized. Although, the DFT approach does not appear to be suitable for the computation of the electronic structure of the isolated Cu(2)O(2) central core, competitive self interaction mechanisms lead to an imperfect but acceptable model when using imidazol ligands. Our results confirm to a certain extent the observations of [M.F. Rode, H.J. Werner, Theoretical Chemistry Accounts 4-5 (2005) 247.] who found a qualitative agreement between B3LYP and localized MRCI calculations when dealing with the Cu(2)O(2) central core with six ammonia ligands.     

Copper(II) hexaaza macrocyclic binuclear complexes obtained from the reaction of their copper(I) derivates and molecular dioxygen

Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III). For those complexes, the singlet state has also been shown to be more stable than the triplet state. In the case of 8c, the most favored structure is the trans-1,2-peroxodicopper(II) because of the para substitution and the steric encumbrance produced by the methylation of the N atoms. Cu(II) complexes 4e, 5e, and 8e have been obtained by O2 oxidation of their corresponding Cu(I) complexes and structurally and magnetically characterized. X-ray single-crystal structures for those complexes have been solved, and they show three completely different types of Cu(II)2 structures: (a) For 4e, the Cu(II) centers are bridged by a phenolate group and an external hydroxide ligand. The phenolate group is generated from the evolution of 4c via intramolecular arene hydroxylation. (b) For 5e, the two Cu(II) centers are bridged by two hydroxide ligands. (c) For the 8e case, the Cu(II) centers are ligated to terminally bound hydroxide ligands, rare because of its tendency to bridge. The evolution of complexes 1c-8c toward their oxidized species has also been rationalized by DFT calculations based mainly on their structure and electrophilicity. The structural diversity of the oxidized species is also responsible for a variety of magnetic behavior: (a) strong antiferromagnetic (AF) coupling with J = -482.0 cm(-1) (g = 2.30; rho = 0.032; R = 5.6 x 10(-3)) for 4e; (b) AF coupling with J = -286.3 cm(-1) (g = 2.07; rho = 0.064; R = 2.6 x 10(-3)) for 5e; (c) an uncoupled Cu(II)2 complex for 8e.     

食品中铜、铅、锡的微分电位溶出法同时测定

用微分电位溶出分析法,以pH2.4的0.06mol·L     

Unimolecular reactivity of strong metal-cation complexes in the gas phase: ethylenediamine-Cu(+)

The gas-phase reactions between ethylenediamine (en) and Cu(+) have been investigated by means of mass spectrometry techniques. The MIKE spectrum reveals that the adduct ions [Cu(+)(H(2)NCH(2)CH(2)NH(2))] spontaneously decompose by loosing H(2), NH(3) and HCu, the loss of hydrogen being clearly dominant. The spectra of the fully C-deuterated species show the loss of HD, NH(3) and CuD but no losses of H(2), D(2), NH(2)D, NHD(2), ND(3) or CuH are observed. This clearly excludes hydrogen exchange between the methylene and the amino groups as possible mechanisms for the loss of ammonia. Conversely, methylene hydrogen atoms are clearly involved in the loss of molecular hydrogen. The structures and bonding characteristics of the Cu(+)(en) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by DFT calculations carried out at B3LYP/6-311+G(2df,2p)//B3LYP/6-311G(d,p) level. Based on the topology of this PES the most plausible mechanisms for the aforementioned unimolecular fragmentations are proposed. Our theoretical estimates indicate that Cu(+) strongly binds to en, by forming a chelated structure in which Cu(+) is bridging between both amino groups. The binding energy is quite high (84 kcal mol(-1)), but also the products of the unimolecular decomposition of Cu(+)(en) complexes are strongly bound Cu(+)-complexes.