微量元素与精神病的研究

一些基础医学实验研究和临床观察的资料表明，精神疾病患者体内的微量元素存在着显著的异常，已引起了国内外学者广泛关注，本文根据近年来的国内外文献报道，概述了微量元素锌（Ｚｎ），铜（Ｃｕ），铁（Ｆｅ）和常量元素钙（Ｃａ），镁（Ｍｇ）的生理作用及与精神病关系的研究进展。     

手性八配位镧系络合物的立体化学与固体CD光谱

本文立体选择性地合成了八配位Ln（III）络合物[Eu（dbm）3L^RR]（1）、[Eu（dbm）3L^SS]（2）和[Tb（dbm）3L^RR]（3）（L^RR／L^SS=（-）／（＋）-4,5-蒎烯基联吡啶,Hdbm=二苯甲酰甲烷）,利用单晶衍射、Uv-vis和固体CD光谱对其进行了表征．晶体结构分析和固体CD光谱表明1和2互为对映体．采用激子手性方法,通过与六配位和七配位的β-二酮络合物的固体CD光谱的对比,提出含β-二酮的八配位Ln（III）络合物的绝对构型关联规则．该系列络合物的畸变四方反棱柱的△或∧绝对构型也被其单晶结构所证实．     

冠心病患者全血微量元素锌、铜、铁的分析

用原子吸收法测定５０例健康人、５２例冠心病患者全血微量元素锌、铜、铁的含量，并对５２例冠心病患者全血微量元素锌、铜、铁的含量及锌／铜比值，与其血脂总胆固醇（ＣＨ）、甘油三酯（ＴＧ）、高密度脂蛋白（ＨＤＬ）、低密度脂蛋白（ＬＤＬ）的浓度分别作线性相关分析。结果表明：（１）冠心病患者全血锌、铁、锌／铜比值均高于健康人（Ｐ＜０．０５），全血铜低于健康人（Ｐ＜０．０５）。（２）全血锌与ＨＤＬ呈负相关（Ｐ＜０．０１）、锌／铜比值与总胆固醇呈正相关（Ｐ＜０．０５），铁与ＬＤＬ呈正相关（Ｐ＜０．０１）．提示锌／铜比值增高及体内铁储存增加均可能是冠心病易患因素．     

脊髓小脑变性疾病病人血清铜,锌,铝,铁含量的研究

脊髓小脑变性疾病（ＳＣＤ）的病因可能与遗传、神经生化紊乱、感染、微量元素平衡障碍及自由基损伤等因素有关，其中微量元素平衡障碍的研究具有重要意义。检测了ＳＣＤ中发病率较高的橄榄桥小脑萎缩症（ＯＰＣＡ）及晚发性小脑皮质萎缩症（ＬＣＣＡ）病人１５例血清中铜、锌、铝、铁等微量元素含量。发现病人比对照组铜明显降低，Ｐ〈０．０１；锌明显降低，Ｐ〈０．０１；铝明显升高，Ｐ〈０．０１；铁无明显差别。     

微量元素缺乏症及其防治

报道了以235名健康小儿的血清锌、铜正常参考值及铜／锌比值作依据，对538名本地区集体儿童进行了调查．对240例不同病种患儿的血清锌、铜含量测定，并进行了分析；对G6PD、GSH-PX、AKP醇活性与微量元素含量的关系进行了相关性比较；对微量元素锌缺乏症的患儿进行了临床治疗观察；对微量元素缺乏症的防治进行了讨论．     

糖尿病人血清与尿中微量元素变化与营养保健的探讨

通过对１１７例糖尿病人血清及尿液分析：发现血清中铜、铁、锌、镁四元素明显低于正常人对照组，差异极为显著（Ｐ＜０．００１）；尿中２４小时排出总量除铁元素无差异外，其他三元素都明显高于正常人对照组（Ｐ＜０．００１）。铜、锌的排出总量是正常人２倍以上，伴随糖尿病增加重随之进一步增加，而血清中铜、锌的含量却随之进一步减少，呈负相关趋势．进而又加重了体内微量元素的缺乏．铜、锌是人体多种酶数的辅基成份或激活因子，对丘脑至靶器官等各级内分泌组组分泌激素有着重要的作用．在常规治疗中补充铜、锌营养对促进糖尿病患者的康复有重要的作用．     

双手性氨基醇水杨醛Schiff碱铜络合物构型与环丙烷化反应立体选择性的关系

利用去甲麻黄素及假去甲麻黄素为手性源，合成了３个水杨醛Ｓｃｈｉｆｆ碱铜（Ⅱ）络合物，并将其应用于烯烃与重氮乙酸乙酯的环丙烷比反应，结果表明：此类铜（Ⅱ）络合物催化环丙烷反应可得到光学异构体过量的产物，络合物中与氮相连的碳原子构型对产物的构型起决定作用，与氧相连的碳原子构型不起决定作用，但对手性诱导能力产生较大的影响；两个手性碳原子构型相异时对手性诱导能力起促进作用，相同时起削弱作用．     

铜—黄嘌呤核苷络合物极谱伏安行为的研究

铜－黄嘌呤核苷络合物极谱伏安行为的研究①樊惠芝刘金龙②潘景浩＊（山西大学化学系太原０３０００６）黄嘌呤核苷（ｘａｎｔｈｏｓｉｎｅ）是重要的生物大分子之一，前人曾用分光光度法、薄层色谱法、纸层色谱法等方法对其进行了定性、定量分析；用ＰＧＥ电极对其电化学...     

（η^2—C60）[Pt（PPh3）2]8的合成与表征

C60是高度共轭的宠状结构碳素体．分子结构中六元环间的共价碳碳双键是富电子区，其反应性能与烯键类似，以碳碳双键与中心金属形成η2配位化合物．富勒烯η2配合物的合成及性能研究是当前研究热点之一[1~7]．本文在（η2-C60）［Pt（PPh3）2］n（n=1～6）系列研究[7]的基础上制备了（η2－C60）［Pt（PPh3）2］8，并用元素分析、红外光谱和光电子能谱进行鉴定和表征．1实验部分四（三苯基膦）合铂Pt（PPh3）4按文献[8]方法制备；C60纯度为99％；其余试剂均为分析纯．元素分析在ERLA－1106型元素分析仪上进行；光电子能谱在VGESCA…     

离子缔合物二级散射光谱的分析应用 Ⅲ.汞(Ⅱ)-硫氰酸盐-罗丹明染料体系

本文研究[Hg（SCN）4]2-络阴离子与罗丹明B和罗丹明6G离子缔合络合物的二级散射（DS）和“反二级散射”（ADS）光谱，考察了光谱特征、影响因素及适宜的反应条件；确定了DS和ADS强度与溶液中汞（Ⅱ）浓度的关系；提出了用ADS法测定痕量汞的新的高灵敏度分析方法，并对有关机理作了初步的探讨。     

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

The triangular cluster [Mo3Se4(H2O)9]4+ reacts with Cu turnings to give a new heterometallic cuboidal cluster [Mo3CuSe4(H2O)10]4+(purple; UV/Vis lambda(epsilon): 352(3907), 509(2613)). The reaction of [Mo3Se4(H2O)9]4+ with CuCl afforded the 5+ cube [Mo3CuSe4(H2O)10]5+(red; UV/Vis lambda(epsilon): 356(5406), 500(3477)). In contrast, [W3Se4(H2O)9]4+ both with Cu and CuCl gives the 5+ cube, [W3CuSe4(H2O)10]5+(yellow-green; UV/Vis lambda(epsilon): 312(5327), 419(3256) and 628(680)). Cyclic voltammetry of [M3CuQ4(H2O)10]5+ in 2 M HCl (M = Mo, W; Q = S, Se) shows a reversible one-electron reduction wave for the Mo clusters, but no reduction occurs for the W clusters prior to H+ reduction. In HCl solutions, Cl is coordinated to the Cu site of the clusters, alongside some less extensive coordination to Mo and W, and for [W3(CuCl)S4(H2O)6Cl3]+, isolated as the supramolecular adduct with cucurbit[6]uril, [W3(CuCl)S4(H2O)6Cl3]2Cl2 x C36H36N24O12 x 12H2O, the crystal structure was determined (Cu-W 2.856(4) angstroms, W-W 2.7432(15) angstroms, Cu-Cl 2.167(13) angstroms).     

A nonanuclear copper(II) polyoxometalate assembled around a mu-1,1,1,3,3,3-azido ligand and its parent tetranuclear complex

Reaction of Cu(II), [gamma-SiW10O36]8-, and N3- affords three azido polyoxotungstate complexes. Two of them have been characterized by single-crystal X-ray diffraction. Complex KNaCs10[{gamma-SiW10O36Cu2(H2O)(N3)2}2].26H2O (1) is obtained as crystals in few hours after addition of CsCl. This linear tetranuclear Cu(II) complex consists in two [gamma-SiW10O36Cu2(H2O)(N3)2]6- units connected through two W=O bridges. When the filtrate is left to stand for one night, a new complex is obtained. From both elemental analysis and IR spectroscopy, it has been postulated that this compound could be formulated K(1.5)Cs(5.5)[SiW10O37Cu2(H2O)2(N3)].14 H2O (1 a), showing the loss of one azido ligand per polyoxometalate unit. Finally, when no cesium salt is added to the reaction medium, the nonanuclear complex K12Na7[{SiW8O31Cu3(OH)(H2O)2(N3)}3(N3)].24 H2O (2) is obtained after three days. Compound 2 crystallizes in the R3c space group and consists in three {Cu3} units related by a C3 axis passing through the exceptional mu-1,1,1,3,3,3-azido bridging ligand. Each trinuclear Cu(II) unit is embedded in the [gamma-SiW8O31]10- ligand, an unprecedented tetravacant polyoxometalate, showing that partial decomposition of the [gamma-SiW10O36]8- precursor occurs with time in such experimental conditions. Magnetically, complex 1 behaves as two isolated {Cu2(mu(1,1)-N3)2} pairs in which the metal centers are strongly ferromagnetically coupled (J = +224 cm(-1), g = 2.20), the coupling through the W=O bridges being negligible. The magnetic behavior of complex 2 has also been studied. Relatively weak ferromagnetic couplings (J1 = +1.0 cm(-1), J2 = +20.0 cm(-1), g=2.17) have been found inside the {Cu3} units, while the intertrimeric magnetic interactions occurring through the hexadentate azido ligand have been found to be antiferromagnetic (J3 = -5.4 cm(-1)) and ferromagnetic (J4 = +1.3 cm(-1)) with respect to the end-to-end and end-on azido-bridged Cu(II) pairs, respectively.     

New routes to polymetallic clusters: fluoride-based tri-, deca-, and hexaicosametallic MnIII clusters and their magnetic properties

The syntheses, structures and magnetic properties of three new MnIII clusters, [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1), [Mn(0O6(OH)2(bta)8(py)8F8] (2) and [NHEt3]2[Mn3O(bta)6F3] (3), are reported (bta=anion of benzotriazole), thereby demonstrating the utility of MnF3 as a new synthon in Mn cluster chemistry. The "melt" reaction (100 degrees C) between MnF(3) and benzotriazole (btaH, C6H5N3) under an inert atmosphere, followed by dissolution in MeOH produces the cluster [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1) after two weeks. Complex 1 crystallizes in the triclinic space group P1, and consists of a complicated array of metal tetrahedra linked by mu3-O2- ions, mu3- and mu2-OH- ions, mu2-MeO- ions and mu2-bta- ligands. The "simpler" reaction between MnF3 and btaH in boiling MeOH (50 degrees C) also produces complex 1. If this reaction is repeated in the presence of pyridine, the decametallic complex [Mn10O6(OH)2(bta)8(py)8F8] (2) is produced. Complex 2 crystallizes in the triclinic space group P1 and consists of a "supertetrahedral" [Mn(III)10] core bridged by six mu3-O2- ions, two mu3-OH- ions, four mu2-F- ions and eight mu2-bta- ions. The replacement of pyridine by triethylamine in the same reaction scheme produces the trimetallic species [NHEt3]2[Mn3O(bta)6F3] (3). Complex 3 crystallises in the monoclinic space group P2(1)/c and has a structure analogous to that of the basic metal carboxylates of general formula [M3O(RCO2)6L3]0/+, which consists of an oxo-centred metal triangle with mu2-bta- ligands bridging each edge of the triangle and the fluoride ions acting as the terminal ligands. DC magnetic susceptibility measurements in the 300-1.8 K and 0.1-7 T ranges were investigated for all three complexes. For each, the value of chi(M)T decreases with decreasing temperatures; this indicates the presence of dominant antiferromagnetic exchange interactions in 1-3. For complex 1, the low-temperature value of chi(M)T is 10 cm(3) K mol(-1) and fitting of the magnetisation data gives S=4, g=2.0 and D=-0.90 cm(-1). For complex 2, the value of chi(M)T falls to a value of approximately 5.0 cm(3) K mol(-1) at 1.8 K, which is consistent with a small spin ground state. For the triangular complex 3, the best fit to the experimental chi(M)T versus T data was obtained for the following parameters: Ja = -5.01 cm(-1), Jb = +9.16 cm(-1) and g=2.00, resulting in an S=2 spin ground state. DFT calculations on 3, however, suggest an S=1 or S=0 ground state with J(a)=-2.95 cm(-1) and J(b)=-2.12 cm(-1). AC susceptibility measurements performed on 1 in the 1.8-4.00 K range show the presence of out-of-phase AC susceptibility signals, but no peaks. Low-temperature single-crystal studies performed on 1 on an array of micro-SQUIDS show the time- and temperature-dependent hysteresis loops indicative of single-molecule magnetism behaviour.     

Halogen exchange and scrambling between C-X and M-X' bonds in copper, nickel, and cobalt complexes of 6,6'-bis(bromo/chloromethyl)-2,2'-bipyridine. structural, electrochemical, and photochemical studies

The synthesis, reactivities, spectroscopic, electrochemical, and structural studies of copper(I), copper(II), nickel(II), and cobalt(II) complexes of 6,6'-bis(bromomethyl)-2,2'-bipyridine (bpy-Br2) and 6,6'-bis(chloromethyl)-2,2'-bipyridine (bpy-Cl2) have been reported. The copper(I) complex [CuI(bpy-Br2)2](ClO4) (1) has been obtained in two crystallographic modifications, in which the coordination geometry of the metal center has the D2d symmetry. The reaction between CuCl2.2H2O and bpy-Br2 has been followed spectrophotometrically at 45 degrees C over a period of 7 h, and a mechanism for the intramolecular halogen exchange and scrambling in the initially formed compound [CuII(bpy-Br2)Cl2] (5) has been proposed. Depending upon the reaction conditions, several halogen-exchanged products, namely [CuII(bpy-Br1.86Cl0.14)(Cl1.89Br0.11)] (2), [CuII(bpy-Br1.81Cl0.19)(Cl1.70Br0.30)(H2O)] (3), and [CuII(bpy-Br0.63Cl1.37)(Cl0.54Br1.46)] (4), have been isolated in crystalline form. The reaction between bpy-Cl2 and CuCl2.2H2O provides [CuII(bpy-Cl2)Cl2] (7) and [CuII(bpy-Cl2)Cl2(H2O)] (8), whereas CoCl2.6H2O and NiCl2.6H20 on reaction with bpy-Br2 under boiling condition produce [CoII(bpy-Br0.5Cl1.5)(ClBr)] (11) and [NiII(bpy-Br0.46Cl1.54)(Cl0.73Br1.27)(H2O)] (12), respectively. The X-ray structures determined for the 4-coordinate compounds 2, 4, and 7 show flattened tetrahedral geometry for the metal center with the D2 symmetry. Both 5-coordinate compounds 3 and 12 have square pyramidal geometry, and whereas the nickel(II) complex 12 has near-perfect geometry (tau = 0.015), considerable distortion is observed for the copper(II) complex 3 (tau = 0.25). Complexes [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] under boiling condition undergo photoreduction to produce the dimeric copper(I) complexes [{CuI(bpy-Cl1.30Br0.70)(mu-Br)}2](9) and [{CuI(bpy-Br2)(mu-Br)}2] (10), respectively. The fact that the photoreduction of [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] do not take place in absence of light has been established by spectrophotometric measurements. The crystal structures of 9 and 10 have been determined. The electrochemical behavior of all the copper complexes 1-10 has been studied in acetonitrile and dichloromethane. The E1/2 values for the CuI/CuII redox couples show strong solvent dependence and for a given system the E1/2 value is more positive in dichloromethane relative to that in acetonitrile. For the compounds [CuII(bpy-Br2-xClx)(Cl2-yBry)] (x = 0-2, y = 0-2), the E1/2 values become more positive with the increase of y value.     

Syntheses, Crystal Structures and NMR of Two Molybdenum Complexes with 2,3-Dihydroxynaphthalene

Two complexes [H3N(CH2)2NH2]2[MoO2(C10H8O2)2] (1) and (C7H10N2)2- [MoO2(C10H8O2)2] (2) were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2(C10H8O2)2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.     

Syntheses, properties and structures of copper and nickel complexes of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate

The reaction of CuCl2-2H2O or NiCl2.6H2O with K2(C5H6S4) [potassium salt of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate] under nitrogen atmosphere resulted in the isolation of [Cu(C5H6S4)2]- or [Ni(C5H6S4)2]- as the tetrabutylammonium salt. Both complexes show characteristic IR and UV-Vis absorptions of transition metal dithiolenes. Cyclic voltammograms contain two waves indicating a two step electrochemical procedure [M(C5H6S4)2]0 = [M(C5H6S4)2]1-= [M(C5H6S4)2]2-. Single crystal structure study has been carried out on the nickel complex. Crystal of [Bu4N][Ni(C5H6S4)2] belongs to monoclinic space group P21/c with a=17.576(5), 6=10.883(2), c=17.773(4) A,B=91.07(2)0, Z=4, and o(calcd.)=1.348 g/cm3. Final result is R=0.059 for 2959 reflections. The NiS4 core exhibits square planar coordination with average Ni-S bond length of 2.134(5) A. There are not anion pairs in crystal. The anions stack along a and c axes while the cations intercalate in them. The nearest S-S contact is 4.429 A. The solid powder ESR s     

Chlorine anion encapsulation by molecular capsules based on cucurbit[5]uril and decamethylcucurbit[5]uril

Three barrel-shaped artificial molecular capsules 1-3, based on normal cucurbit[5]uril (Q[5]) and decamethylcucurbit[5]uril (Me10Q[5]), were synthesized and structurally characterized by single-crystal X-ray diffraction. Encapsulation of a chlorine anion in the cavity of a Q[5] or Me10Q[5] to form closed a molecular capsule with the coordinated metal ions or coordinated metal ions and water molecules in the crystal structures of these compounds is common. The three complexes [Pr2(C30H30N20O10)Cl3(H2O)13]3+ 3 Cl- x 5 H2O (1), [Sr2(C40H50N20O10)(H2O)4Cl]3+ 3 Cl- x 2 (HCl) 19 H2O (2) and [K(C40H50N20O10)(H2O)Cl] x [Zn(H2O)2Cl2] x [ZnCl4]2- x 2 (H3O)+ x 8 H2O (3) all crystallize as isolated molecular capsules.     

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. a series of novel polyoxotungstates sandwiched by octa-copper clusters

The reaction of CuCl(2).2 H2O with trivacant Keggin polyoxoanions K8Na2[A-alpha-GeW9O34].25 H2O or K10[A-alpha-SiW9O34].25 H2O in the presence of 1,2-diaminopropane (dap), ethylenediamine (en) or 2,2'-bipyridine (2,2'-bpy) under hydrothermal conditions afforded five novel hybrid inorganic-organic octa-Cu sandwiched polyoxotungstates (POTs): H4[CuII8(dap)4(H2O)2(B-alpha-GeW9O34)2].13 H2O (1), (H2en)2[CuII8-(en)4(H2O)2(B-alpha-GeW9O34)2].5 H2O(2), (H2en)2[CuII8(en)4(H2O)2(B-alpha-SiW9-O34)2].8 H2O (3), [CuII(H2O)2]H2[CuII8-(en)4(H2O)2(B-alpha-SiW9O34)2] (4), and [CuII2(H2O)2(2,2'-bpy)2]{[CuII(bdyl)]2-[CuII8(2,2'-bpy)4(H2O)2(B-alpha-GeW9-O34)2]}.4 H2O (bdyl=2,2'-bipyridinyl)(5). Additionally, CuCl(2).2 H2O reacts with the mixture of GeO2, Na2WO(4).2 H2O, H2SiW12O(40).2 H2O in the presence of 2,2'-bpy and 4,4'-bpy under hydrothermal conditions leading to another novel mixed-valent octa-Cu sandwiched POT hybrid: [CuI(2,2'-bpy)(4,4'-bpy)]2[{CuI2(2,2'-bpy)2(4,4'-bpy)]2[CuI2CuII6(2,2'-bpy)2(4,4'-bpy)2(B-alpha-GeW9O34)2}].2 H2O (6). 1, 2, and 3 are discrete dimers constructed from two trivacant Keggin [B-alpha-XW9O34]10- (X=GeIV/SiIV) fragments and an octa-Cu cluster whereas 4 displays the 3D (3,6)-connected nets with (4.6(2))(4(2).6(4).8(7).10(2)) topology, which are built by octa-Cu sandwiched polyoxometalate building blocks through copper cation bridges. 5 is a novel 2D layer based on octa-Cu sandwiched POT clusters and [CuII2(bdyl)] units. Interestingly, the rollover metalation of 2,2'-bpy is firstly observed in the system containing the copper complex under hydrothermal conditions. 6 is a discrete mixed-valent octa-Cu sandwiched POT supported by two CuI-complexes [CuI2-(2,2'-bpy)2(4,4'-bpy)]2+ through 4,4'-bpy bridges, which constructs a novel dodeca-copper cluster. Notably, the octa-Cu cluster in 6 is mixed-valent and is different from those in 1-5. To our knowledge, 1-6 represent a rare family of POTs incorporating novel octa-nuclear transition-metal clusters in polyoxometalate chemistry. They were structurally characterized by FT-IR spectra, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. The magnetic properties of 1, 4, and 5 were quantitatively analyzed by the MAGPACK software package.     

A New Coordinated Transition-metal Linked Network Compound Constructed by Octamolybdate Chain

1 INTRODUCTION The polyoxometalates have aroused extensive in-terest due to their alluring topologies and potentialapplications in various fields (e.g. catalysis, biology,medicine and materials science)[1]. A variety of po-lyoxometalate anions and related fragments withoxygen-rich compositions can serve as inorganic li-gands to coordinate secondary transition metal ions(so-called heterometals, such as Cu2 , Ni2 , Co2 andMn2 )[2]. Thus, larger discrete species and infinitelyextending ar…     

Structural and functional characteristics of rhenium clusters derived from redox chemistry of the triangular [ReIII3(mu-Cl)3] core unit

The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3(8+) core. Dissolution of 1 in HCl (6 M) generates [Re3(mu-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6-12 M) produces [(C6H5)4P]2[Re3(mu-Cl)3Cl7(H2O)2].H2O (3), the structure of which features a planar [Re3(mu-Cl)3Cl3] framework (Re3(8+) core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3(8+)-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-OH))2].2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3(9+) triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-Cl))2].10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1-3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(mu-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(mu-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(mu-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3(8+) cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(mu-Cl)3Cl7(CH3C(O)NH)].CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(mu-Cl)3Cl8(MeOH)].MeOH (10).