Synthesis, Characterization and Crystal Structures of Some Linked Metal Carbonyl Clusters Derived from Diethynyl-Substituted Silane and Disilane Ligands

The use of diethynylsilane, diethynyldisilane and diethynyldisiloxane in the synthesis of some linked metal carbonyl clusters is demonstrated. New dimeric η²-diyne complexes of cobalt [{Co₂(CO)₆}₂(η²-diyne)], ruthenium [{(μ-H)Ru₃(CO)₉}₂(μ₃-η²,η²-diyne)] and osmium [{(μ-CO)Os₃(CO)₉}₂(μ₃-η²-diyne)] {diyne=HC≡CSi(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–Si(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–O–Si(CH₃)₂C≡CH or HC≡CSi(Ph)₂C≡CH} have been prepared in good yields from the reaction of [Co₂(CO)₈], [Ru₃(CO)₁₂] and [Os₃(CO)₁₀(NCMe)₂] with half an equivalent of the appropriate diyne ligand, respectively. All the twelve compounds have been characterized by IR and ¹H NMR spectroscopies and mass spectrometry. The molecular structures of eight of them have been determined by X-ray crystallography. Structurally, each of the tetracobalt species displays two Co₂C₂ cores adopting the pseudo-tetrahedral geometry with the alkyne bond lying essentially perpendicular to the Co–Co vector. For the group 8 ruthenium and osmium analogues, the hexanuclear carbonyl clusters consist of two trinuclear metal cores with the μ₃-η²,η² bonding mode for the acetylene groups in the former case and μ₃-(η²-||) bonding mode in the latter one. Density functional theory was employed to study the electronic structures of these molecules in terms of the nature of the silyl or disilyl unit and its substituents.     

The Synthesis and Spectroscopic Characterization of Heterobimetallic Bu2Sn(IV) Complexes Derived from Some Chelating Ligands

The interaction of Bu₂Sn(OPrⁱ)₂ with a trifunctional tetradentate Schiff base (LH₃) (where H₃L = HOC₆H₄CH═NCH₃C(CH₂OH)₂) yields the precursor complex Bu₂Sn(LH) 1, which, on equimolar reactions with different metal alkoxides [Al(OPrⁱ)₃, Bu₃Sn(OPrⁱ), Ge(OEt)₄]; Al(Medea)(OPrⁱ) (where Medea = CH₃N- (CH₂CH₂O)₂); and Me₃SiCl in the presence of Et₃N], affords, respectively, the complexes Bu₂Sn(L)Al(OPrⁱ)₂ 2, Bu₂Sn(L)Al(Medea) 3, Bu₂Sn(L)Bu₃Sn 4, Bu₂Sn(L)Ge(OEt)₃ 5, and Bu₂Sn(L)SiMe₃ 6. The reactions of 2 with 2,5-dimethyl-2,5-hexanediol in a 1:1 ratio and with acetylacetone (acacH) in a 1:2 molar ratio afforded derivatives Bu₂Sn(L)Al(OC(CH₃)₂CH₂CH₂C(CH₃)₂ O) 7 and Bu₂Sn(L)Al(acac)₂ 8, respectively. All of the derivatives 1– 8 have been characterized by elemental analyses, molecular weight measurements, and spectroscopic [IR and NMR (¹H, ¹¹⁹Sn, ²⁹Si, and ²⁷Al)] studies.     

Synthesis,Characterization and Crystal Structures of New Difurylphosphido-bridged Dinuclear Ruthenium Carbonyl Complexes Derived from Ferrocenylacetylene Ligands

The difurylphosphido-bridged dinuclear complex [Ru₂(CO)₆(μ-PFu₂)(μ-η¹,η²-Fu)] (Fu = 2-furyl) 1 readily reacts with two equivalents of each of the terminal alkynes HC≡CR (R = Fc, p-C₆H₄Fc, p-C₆H₄NO₂, Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄)) by an interesting head-to-tail ynyl coupling with a furan group to form a series of phosphido-bridged diruthenium compounds containing a novel furyl-substituted C₄ hydrocarbyl chain of stoichiometry [Ru₂(CO)₄(μ-PFu₂){μ-η¹,η¹,η²,η³-RCC(H)C(R)C(H)Fu}] (R = Fc 2, p-C₆H₄Fc 3, p-C₆H₄NO₂ 4) in moderate to good yields. Reaction of 1 with an equimolar amount of HC≡CFc and HC≡C(p-C₆H₄NO₂) afforded a pair of isomers of [Ru₂(CO)₄(μ-PFu₂){μ-η¹,η¹,η²,η³-R¹CC(H)C(R²)C(H)Fu}] (R¹ = Fc, R² = p-C₆H₄NO₂ 5a; R¹ = p-C₆H₄NO₂, R² = Fc 5b) together with a small mixture of 4. X-ray crystal structures of 2, 3, 5a and 5b are reported. All of these new alkyne-derived dinuclear complexes are electron precise with 34 cluster valence electrons in which the μ-η¹,η²-furyl ligand acts as a three-electron donor and the μ-phosphido Ru₂ framework is retained in the products upon alkyne coupling reactions. The resulting organic fragment of each complex is coordinated to the Ru atoms via a π, a π-allyl and two σ bonds, and donates seven electrons to the metal core. Dedicated to the memory of Professor F. Albert Cotton.     

异金属配合物的合成、表征与光谱性质

以多氨羧酸为配体,在水溶液中合成了两个同时含Bi3+和Eu3+两种金属的晶态配合物BiEu(edta)(NO3)2·6.5H2O和非晶态配合物BiEu(dtpa)(NO3)·4(H2O).采用元素分析仪、红外光谱仪、X射线粉末衍射仪等手段对产物进行表征.采用热分析仪对产物的热稳定性进行了研究.室温下采用紫外可见光度计和荧光光谱仪对固态产物的光学性质进行测试,结果显示产物既发Eu3+的线状特征荧光,又发Bi3+的带状荧光.     

Synthesis,Characterization and Crystal Structures of New Ruthenium Carbonyl Clusters Derived from (9-Anthracenyl)diphenylphosphine*

Thermal reaction of [Ru₂(CO)₆(μ-PFu₂)(μ-η¹,η²-Fu)] (Fu=2-furyl) with (9-anthracenyl)diphenylphosphine (AnPPh₂) produces a novel diruthenium complex [Ru₂(CO)₅(μ-PFu₂)(μ-η¹,η¹,η²-C₁₄H₈PPh₂)] (1) in good yield whereas the corresponding reaction between [(μ-H)₄Ru₄(CO)₁₂] and AnPPh₂ gives [HRu(CO)₃(PPh₂C₁₄H₈)][(μ-H)₄Ru₄(CO)₁₁(AnPPh₂)] (2). Both compounds 1 and 2 were fully characterized by spectroscopic methods and their X-ray crystal structures were determined. For 1, initial coordination of the PPh₂ functionality at the Ru atom is accompanied by cyclometalation of the anthracenyl ring to form a Ru–C σ bond together with concomitant formation of a π bond to the adjacent Ru center and loss of the furyl ligand. The formation of 2 involves the cleavage of two Ru–Ru bonds, and the making of a Ru–P bond, followed by orthometalation of the anthracenyl ring. The optical absorption and emission spectra of 1 were recorded and the results were correlated to the DFT calculations.Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday.     

RP-Bridged Metal Carbonyl Clusters: Synthesis,Properties, and Reactions

Metal carbonyl clusters possess a complicated chemistry that is only beginning to be understood. One of the main current goals in this area is thus an understanding of their reactivity. This article describes the syntheses and reactions of clusters that contain metal carbonyl fragments bridged by a main-group element. But what is the sense of making such clusters still more complicated by the incorporation of main-group elements? The example of μ₃-bridged carbonyl clusters will serve to show that the main-group element plays an important role in the study of reaction paths; it holds the metal carbonyl fragments together even when the bonds between them are broken in the course of a reaction. Trinuclear μ₃-bridged clusters prove to be small enough to allow the analysis of typical cluster reactions (such as the reversible breaking of metal-metal bonds) in terms of single reaction steps. They are also large enough to provide surprises by their multifaceted reactivity. It will be shown that a detailed study of trinuclear RX-bridged metal carbonyl clusters (X ? N, P, As, Sb, Bi)—a very small part of carbonyl cluster chemistry—can lead to a better understanding of the general reaction principles involved.     

Synthesis and Structural Characterization of Some Potassium Complexes of Some Bis(phenolate) Ligands and Some Novel Heterobimetallic Binuclear Arrays Formed with Trivalent Lanthanoid Ions

The structural characterizations of the potassium complexes of a pair of dianionic bis(phenolate) ligands, {L^R = [^?OC₆H₂(2,4‐Bu^t)(6‐CH₂)]₂NCH₂CH₂R} R = NMe₂, OMe, crystallized from 1,2,‐dimethoxyethane (DME) are recorded, showing them to take the binuclear form [K₂L^R(DME)₃]. A pair of neutral binuclear heterobimetallic isotypic complexes are defined with ytterbium(III), with phenol, as sodium salts, of the form [Yb(L^R)(OPh)₂Na(DME)(HOPh)], and a further array with samarium(III), of the (partially protonated) form [Sm(L^OMe)₂Na(OH₂)]. A further complex, [Na(DME)₃][Yb(*L^py)₂], results from an unusual ligand reduction by an ytterbium(II) species to give a new dianionic Schiff base ligand which is coordinated to ytterbium(III) {*L^py = ^?OC₆H₂(2,4‐Bu^t)(6‐CH=N‐CH‐2‐C₆H₄N)}.     

Synthesis,Structural Characterization and Properties of Two Strontium Borates Constructed from Oxo Boron Clusters

Two strontium borates Sr₂[B₆O₉(OH)₄] (1) and Sr₂B₅O₉(OH)·H₂O (2), with acentric structures have been synthesized under hydro/solvothermal conditions. Compound 1 is reported for the first time in the strontium borates system, and it crystallizes in the monoclinic space group P2₁ with unit cell parameters a = 6.8445(5) Å, b = 8.7033(6) Å, c = 8.4632(6) Å, β = 100.581(6)°, V = 495.58(6) ų and Z = 2. Its structure consists of unusual borate layers of 3, 11-membered rings, which are interconnected via Sr–O ionic bonds and hydrogen bonds to generate a 3D supramolecular network. Compound 2 is a known strontium borate, crystallizing in the monoclinic space group C ₂ with a = 10.161 (13) Å, b = 7.965(4) Å, c = 6.393(11) Å, β = 128.0(2)°, V = 407.7(14) ų and Z = 2. Second-harmonic generation measurements on the powder samples reveal that 1 and 2 exhibits good SHG efficiency about 1.5 and 2 times that of KDP (KH₂PO₄) powder respectively.     

Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry

Two new tetraosmium carbonyl clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (1) and [Os₄(-H)₄(CO)₁₀{ ²-NC₅H₄(N=N)C₆H₅}] (2) were synthesized from the reaction of [Os₄(-H)₄(CO)₁₂] with two equivalent of 2-phenylazopyridine ligand in dichloromethane at ambient temperature using trimethylamine-N-oxide as the decarbonylation reagent. Subsequent chromatographic purification led to the isolation of 1and 2as stable orange and blue solids in respectively 25 and 13% yields. Complex 1converted to 2in a 25% yield in refluxing chloroform. Treating a solution of [Os₄(-H)₄(CO)₁₂] in dichloromethane with two equivalent of 3-phenylazopyridine led to the formation of another two new clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (3) and [Os₄(-H)₄(CO)₁₀(NMe₃){ ¹-NC₅H₄(N=N)C₆H₅}] (4), which could be isolated as yellow solids in 34% and 21% yields respectively. Thermolysis of 3or 4in refluxing n-hexane gives [Os₄(-H)₃(CO)₁₀{- ³-NC₅H₃(N=N)C₆H₅}] (5) in 24 and 33% yields respectively. Their electronic absorption properties and electrochemical behavior are also reported.     

Chalcogen-Containing Manganese Carbonyl Clusters: Synthesis and Structural Transformations

Recently, we have developed several synthetic routes to the new classes of chalcogen-containing manganese carbonyl clusters, and the interesting structural transformations and reactivity of the resultant clusters have been investigated as well. In this short review, the syntheses and bonding modes of the sulfur, selenium, and tellurium-containing manganese carbonyl complexes reported by our laboratory will be presented, and the cluster growth and transformation will be systematically compared and discussed.     

由分子筛笼内铂羰基簇合物得到的催化剂的分散度研究

由分子筛笼内包容的铂羰基簇合物[Pt_(12)(CO)_(24)]~(2-)/NaY和[Pt_9(CO)_(18)]~(2-)/NaY经还原得到的样品Pt_(12)/NaY和Pi_9/NaY的分散度用EXAFS和化学吸附进行了表征．对Pt_(12)/NaY和Pi_9/NaY，EXAFS分析分别给出R_(Pt－Pt)＝0.274 nm，配位数C.N.＝0.42和R_(Pt－Pt)＝0.274 nm配位数C.N.＝3.8，而化学吸附结果分别为H/Pt＝1.26，CO/Pt＝0.69和H/Pt＝1.24，CO/Pt＝0.64．与浸渍法制备的Pt/Al_2O_3相比小得多的Pt－Pt配位数及大的化学吸附值说明，由分子筛笼内铂羰基簇合物出发，我们得到了高分散的Pt/NaY催化剂．由于还原后原子堆积形式的变化，Pt_(12)/NaY和Pt_9/NaY的再还原羰基化不能可逆地得到与前驱体相同的铂羰基簇合物．     

结构不对称三芳胺类化合物的合成、表征及性质研究

以二芳胺和3,5-二甲基碘苯为原料,利用乌尔曼(Ullmann)反应,合成出了4个结构不对称三芳胺衍生物1～4,除了化合物1之外均为新化合物.利用IR,1H NMR,13C NMR,HRMS和元素分析对其结构进行了表征.考察了它们的光学、电化学和热稳定性质.实验结果表明,所合成的4个目标化合物在氯仿稀溶液中发出绿色荧光,具有良好的电化学和热稳定性.所合成的目标化合物是潜在的空穴传输材料及发绿光的材料.     

Synthesis and Metal-Binding Properties of Polybipyridine Ligands Derived from Acyclic and Macrocyclic Polyamines

Synthetic procedures have been developed for the preparation of ligands bearing two to six pendent, unsubstituted or substituted 2, 2′-bipyridine groups attached to acyclic (tripode, tetrapode) and macrocyclic (triazanonade-cane, cyclam, hexacyclen, bis(bipyrido)hexaazamacrocycle) polyamines. Ligands 1-5 have been obtained in high yield by condensation of 6-(bromomethyl)-2, 2′-bipyridine ( 9b ) with the corresponding amines in the presence of NaOH, H₂O, and MeOH. Ligands 6-8 have been prepared in good yield by condensation of 9b or the di- or tetrasubstituted mono (bromomethyl) bipyridine 10b or 11b , respectively, with the corresponding amines in the presence of Na₂CO₃ and MeCN. Ligand 1 forms hemi-cage complexes with Ru^II, Fe^I, Cr^II, and Cr^III cations and trinuclear complexes with [RuCl²(bpy)²] and [ReCl(CO)⁵]. Tetrapode 2 and hexapode 4 gave tetranuclear and dinuclear complexes, respectively, by reaction with Fe11 salts. These complexes possess a variety of interesting physical and chemical properties.     

手性金属簇合物的合成、结构表征及其反应

用潜手性羰基簇合物 ( μ3 S)RuCo2 (CO) 9( 1 )与阴离子金属交换试剂Na[M (CO) 3C5 H4C(O)R][R =H ,CH3,C6 H5 ,C6 H4C(O)OCH3;M =Mo ,W ]在四氢呋喃中回流反应 ,生成一系列新的由四个不同原子组成的不对称四面体簇合物 ( μ3 S)RuCoM (CO ) 8CpCOR .研究了簇合物 ( μ3 S)RuCoMo(CO) 8CpCOCH3的还原反应 .对合成的所有化合物进行了IR、1HNMR、C/H元素分析 ,测定了簇合物( μ3 S)RuCoMo(CO) 8CpCOC6 H5 的单晶结构 .     

含樟脑衍生物氰基桥联双金属配合物的合成、结构及磁性质

采用樟脑衍生物为配体，分别合成了氰基桥联Cu(Ⅱ)-Fe(Ⅲ)-Cu(Ⅱ)三核配合物[{Cu(D,L-La)₂}₂Fe(CN)₆](ClO₄) (1)和Mn(Ⅲ)-Fe(Ⅲ)双核配合物[Mn(D,L-Lb)(DMF)(Tp)Fe(CN)₃]·(H₂O)₆ (2)。晶体结构分析表明，化合物1中Cu(Ⅱ)离子处于五配位的配位环境，分别和1个D-La，1个L-La及[Fe(CN)₆]^3-中的1个氰基配位，2个Cu(Ⅱ)离子通过[Fe(CN)₆]^3-桥联。通过分子间氢键作用，化合物1形成二维超分子网络结构。化合物2中，[(Tp)Fe(CN)₃]^-通过其中的1个氰基与[Mn(D，L-Lb)]⁺桥联，其中Mn(Ⅲ)离子为六配位，分别和四齿配体Lb的2个氧原子和2个氮原子、DMF的1个氧原子及[(Tp)Fe(CN)₃]^-中的氰基氮原子配位。磁性研究表明，在化合物1中，Cu(Ⅱ)离子与Fe(Ⅲ)离子之间表现出铁磁相互作用，用哈密顿函数H=-2J(S₁·S₂+S₂·S₃)对其χ_MT-T曲线进行拟合，得到1的朗日因子g为2.190，交换常数J为0.55 cm^-1。     

Synthesis and Characterization of Gold Nanoparticles with Surface Ligands Derived from a Primary Phosphine

Reduction of HAuCl₄ · 3H₂O with NaBH₄ in THF/H₂O in the presence of the primary phosphine PH₂Mes* (Mes* = 2,4,6-(t-Bu)₃C₆H₂) gave a mixture of ca. 1.3 nm diameter gold nanoparticles (1) and the known oligomers [Au(PHMes*)]_n (2). Nanoclusters 1 might contain phosphido (PHMes*) or phosphinidene (PMes*) surface ligands, or both; they were characterized by elemental analysis, TGA, XPS, TEM, NMR, IR, and UV–Vis spectroscopies, and by their reactions with dodecanethiol, which gave PH₂Mes*. Solid-state ³¹P-NMR cross-polarization studies of 1 and 1D (prepared using NaBD₄ and PD₂Mes* in THF/D₂O) were consistent with the presence of phosphinidene surface groups.