C60[RuHCl（CO）（PPh3）]3配合物的合成和表征

富勒烯配合物的制备及其性质的研究是目前富勒烯化学最为活跃的研究领域之一［１］,人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系,以期合成出具有特殊性能的富勒烯配合物,为富勒烯的实际开发应用奠定基础。本文首次合成Ｃ６０［ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）］３配合物,采用元素分析、红外光谱、电子光谱进行鉴定和表征,并推测了其结构。１　实验部分１．１　Ｃ６０［ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）］３的合成合成按下列反应进行：ＲｕＣｌ３＋３ＰＰｈ３＋ＨＣＨＯ→ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）３ＲｕＨＣｌ（…     

(Ph_3P)_2(CO)RuC_(60)的合成及结构表征

过渡金属—Ｃ６０配合物的合成及结构的研究是Ｃ６０化学非常重要的一个组成部分，这对于发展Ｃ６０化学及新型功能材料的开发具有很大意义．关于这方面的研究工作近年已有一些报道〔１～３〕．Ｈａｗｋｉｎｓ等关于（ｔＢｕＣ６Ｈ５Ｎ）２ＯｓＯ４（Ｃ６０）的合成及单...     

杂多阴离子的有机金属化学(Ⅲ)──缺位Keggin阴离子PW_9O_(34)~(9-)的酯基锡杂多配合物的合成及性质

利用酯基锡与缺位Ｋｅｇｇｉｎ结构杂多阴离子ＰＷ９Ｏ９－３４反应，合成了６种新的杂多阴离子有机金属配合物Ｍ９［（Ｒ′ＯＯＣＣＨＲ″ＣＨ２ＳｎＯＨ２）３（ＰＷ９Ｏ３４）２］·ｘＨ２Ｏ（Ｍ＝（ＣＨ３）４Ｎ＋，Ｋ＋；Ｒ′＝ＣＨ３＿，ＣＨ３ＣＨ２＿；Ｒ″＝Ｈ，ＣＨ３＿），通过元素分析、ＩＲ光谱、紫外电子光谱、１ＨＮＭＲ、３１ＰＮＭＰ、１８３ＷＮＭＲ和ＴＧＡ－ＤＳＣ热分析等测试手段对标题配合物进行了表征和性质研究，确定该系列配合物为Ａ－β－ＰＷ９型夹心配合物结构．     

碘·(N,N'联吡啶)·(三苯基膦)合铜(I)的合成和晶体结构

铜（Ｉ）配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义［１］。但由于铜（Ｉ）配合物不稳定,且在多数有机溶剂中的溶解度较小,铜（Ｉ）配合物的合成比较困难。我们在铜（Ｉ）配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜（Ｉ）配合物［ＣｕＸ（ＰＰｈ３）Ｌ］ｎ［２～４］（ｎ＝１,Ｘ＝Ｉ,Ｌ＝１,１０ｐｈｅｎ;ｎ＝２,Ｘ＝Ｂｒ,Ｉ,Ｌ＝Ｃ９Ｈ７Ｎ）,并对它们的结构进行了研究。本文报道一个类似的新配合物［ＣｕＩ（ＰＰｈ３）（ｂｐｙ）］（Ｉ）的合成…     

KI-醚类催化剂催化二氧化碳和环氧乙烷合成碳酸乙烯酯反应研究

合成了５个含有金属铁的环醚Ｆｅ（ＣＯ）３Ｌ（Ｌ１＝Ｐｈ２Ｐ（ＣＨ２ＣＨ２Ｏ）２ＣＨ２ＣＨ２ＰＰｈ２，Ｌ２＝Ｐｈ２Ｐ（ＣＨ２ＣＨ２Ｏ）４ＣＨ２ＣＨ２ＰＰｈ２，Ｌ３＝ＯＰｈ［（ＯＣＨ２ＣＨ２）ＰＰｈ２］２，Ｌ４＝ＯＰｈ［ＯＣＨ２ＣＨ２）２ＰＰｈ２］２）和［Ｆｅ（ＣＯ３）］２Ｌ５（Ｌ５＝［Ｐｈ２ＰＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＰＰｈ２］２）．对它们进行了元素分析，并用红外光谱和核磁共振谱进行了结构表征．用ＫＩ＋醚类为催化剂，催化二氧化碳与环氧乙烷反应生成碳酸乙烯酯，反应选择性大于９６．９％．催化机理为碱催化，催化剂的活性受醚的影响．能和Ｋ＋形成稳定配合物的醚可提高催化剂的活性．含金属铁的环醚和普通醚类相似，可以和钾离子作用，提高阴离子的亲核催化性能．     

FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

三核过渡金属配合物〔M_3~ⅢO(OOCR)_6L_3〕 (M=Cr,Fe,Mn;R=CH_3,C_2H_5,CH_2NH_2;L=C_5H_5N,H_2O)的~1H NMR性质

采用１ＨＮＭＲ谱研究了通式为〔Ｍ３ⅢＯ（ＯＯＣＲ）６Ｌ３〕＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁交换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表明,其１Ｈ各向同性位移主要由接触作用贡献     

钛、锆螺环配合物的合成与表征(英文)

合成了两个新奇的配合物Ｔｉ［Ｏ－Ｐｈ－Ｃ（ＣＨ２ＣＨ３）２－Ｃｐ］２和Ｚｒ［Ｏ－Ｐｈ－Ｃ（ＣＨ２ＣＨ３）２－Ｃｐ］２，对合成的配合物进行了元素分析，ＩＲ，１ＨＮＭＲ和ＭＳ表征。     

铜（Ⅰ）配合物［Cu（C_8H_4O_2F_3S）（PPh_3）_2］合成、性质、晶体结构及反应机理的探讨

铜（Ⅰ）配合物［Ｃｕ（Ｃ８Ｈ４Ｏ２Ｆ３Ｓ）（ＰＰｈ３）２］合成、性质、晶体结构及反应机理的探讨王冬梅杨瑞娜侯益民金斗满＊（河南化学研究所，郑州４５０００３）关键词：铜粉三苯基膦晶体结构铜（Ⅰ）配合物在生理上是绝对重要的。有文献报道铜（Ⅰ）—亚酰配合物...     

三核过渡金属配合物[M3^ⅢO（OOCR）6L3]^＋（M=Cr,Fe,Mn;R=CH3,C2H5,CH …

采用＾１Ｈ ＮＭＲ谱研究了通式为（Ｍ３＾ⅢＯ（ＯＯＣＲ）６Ｌ３）＾＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其＾１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁变换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表     

Linkage and redox isomerism in ruthenium complexes of catecholate, semiquinone, and o-acylphenolate ligands derived from 1,2-dihydroxy-9,10-anthracenedione (alizarin) and related species: syntheses, characterizations, and photophysics

The complexes Ru(CO)2L2(AL-2H) (AL = alizarin; L = PPh3, PCyc3, PBu3, P(m-NaSO3C6H4)3), Ru(CO)(dppe)(PBu3)(AL-2H), and RuH(CO)L2(AL-H) (L = PPh3, PCyc3), and Ru(CO)2L2(AR-2H) (AR = anthrarobin; L = PBu3) were prepared by reactions of Ru3(CO)12, L, and AL, and the complexes RuH(CO)(PPh3)2(AL-H), RuH(CO)(PPh3)2(QN-H) (QN = quinizarin), and RuH(CO)(PPh3)2(LQN-H) (LQN = leucoquinizarin) are prepared by reactions of RuH2(CO)(PPh3)3 with AL or QN. The AL-2H and AR-2H ligands act as 1,2-catecholates, whereas the AL-H, QN-H, LQN-H ligands are 1,9-o-acylphenolate ligands. RuH(CO)(PPh3)2(AL-H) is characterized by X-ray crystallography. The electrochemistry of these complexes is examined, and the semiquinone complexes [Ru(CO)2L2(AL-2H)]+ (L = PPh3, PCyc3, PBu3) and [Ru(CO)(dppe)(PBu3)(AL-2H)]+ are generated by chemical oxidation and were characterized by EPR and IR spectroscopy. The photophysical properties are also reported.     

RuH2(CO)(PPh3)3 catalyzed selective formation of 1,4-disubstituted triazoles from cycloaddition of alkynes and organic azides

The ruthenium hydride complex RuH(2)(CO)(PPh(3))(3) was found to be an effective catalyst for the cycloaddition reactions of terminal alkynes and azides. In the presence of RuH(2)(CO)(PPh(3))(3), various azides reacted with a range of terminal alkynes to produce 1,4-disubstituted 1,2,3-triazoles with 100% selectivity and moderate to excellent yields.     

η2-C60[RhCl(CO)(PPh3)2]配合物的合成与表征

从1985年Smalley等[1]发现C60等富勒烯至1996年富勒烯的发现者获诺贝尔化学奖期间, 在化学、 材料、 物理等领域形成了富勒烯的研究热潮[2～5]. 现在科学工作者正以较大的注意力投向富勒烯的化学修饰, 研究富勒烯各类衍生物的结构与性能之间内在联系规律, 以期望在开发应用方面取得突破性进展, 为此也十分重视对具有特殊组成与结构的富勒烯衍生物的研究. 本文首次合成出η2-C60[RhCl(CO)(PPh3)2]配合物, 并对其结构进行了表征.     

Sigma-organyl complexes of ruthenium and osmium supported by a mixed-donor ligand

A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)2](BTD = 2,1,3-benzothiadiazole) by reaction with the nitrogen-sulfur mixed-donor ligand, 1-methyl-2-mercaptoimidazole (HMI), in the presence of base. In the same manner, [Os(CH=CHPh)(kappa2-MI)(CO)(PPh3)2] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh3)2]. The in situ hydroruthenation of 1-ethynylcyclohexan-1-ol by [RuH(CO)Cl(BTD)(PPh3)2] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC6H9)(kappa2-MI)(CO)(PPh3)2]. Dehydration of the complex [Ru(CH=CHCPh2OH)(kappa2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(kappa2-MI)(CO)(PPh3)2]BF4. The hydride complexes [MH(kappa2-MI)(CO)(PPh3)2](M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh3)3] and [OsHCl(CO)(BTD)(PPh3)2], respectively. Reaction of [Ru(CH=CHC6H4CH3-4)(kappa2-MI)(CO)(PPh3)2] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh3)2] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh = CHPh)Cl(CS)(PPh3)2] reacted with HMI and NaOMe without migration to yield [Ru(CPh= CHPh)(kappa2-MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO)2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa2-MI)(CO)(PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported.     

From amine to ruthenaziridine to azaallyl: unusual transformation of di-(2-pyridylmethyl)amine on ruthenium

The complexation of di-(2-pyridylmethyl)amine to RuHCl(PPh(3))(3) affords the salt [RuH{κ(3)N-fac-1,3-di-(2-pyridylmethyl)amine}(PPh(3))(2)]Cl. Reaction with potassium tert-butoxide at room temperature yields the unusual ruthenaziridine complex RuH{κ(3)C(alk)NN(py)-1,3-di-(2-pyridylmethyl)amine}(PPh(3))(2), where the central nitrogen atom, adjacent alkyl carbon, and pyridine arm coordinate to the metal, leaving the second pyridine arm uncoordinated. Surprisingly, heating of this ruthenaziridine complex with concomitant H(2) formation affords the ruthenium azaallyl complex RuH(κ(3)N-1,3-di-(2-pyridyl)-2-azaallyl)(PPh(3))(2). This is a rare example of a 4d metal complex containing the azaallyl ligand. X-Ray crystal structures and NMR characterization of all three compounds are presented herein.     

Iron Sulfido Derivatives of the Fullerenes C(60) and C(70)

Toluene solutions of C(60) react upon UV irradiation with Fe(2)S(2)(CO)(6) to give C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-6. C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-3 have been isolated and characterized. Crystallographic studies of C(60)S(2)Fe(2)(CO)(6) show that the S-S bond of the Fe(2) reagent is cleaved to give a dithiolate with idealized C(2)(v)() symmetry. The addition occurred at a 6,6 fusion, and the metrical details show that the Fe(2) portion of the molecule resembles C(2)H(4)S(2)Fe(2)(CO)(6). IR spectroscopic measurements indicate that the Fe(2)(CO)(6) subunits in the multiple-addition species (n > 1) interact only weakly. UV-vis spectra of the adducts show a shift to shorter wavelength with addition of each S(2)Fe(2)(CO)(6) unit. Photoaddition of the phosphine complex Fe(2)S(2)(CO)(5)(PPh(3)) to C(60) gave C(60)[S(2)Fe(2)(CO)(5)(PPh(3))](n)(), where n = 1-3. (31)P{(1)H} NMR studies show that the double adduct consists of multiple isomers. Photoaddition of Fe(2)S(2)(CO)(6) to C(70) gave a series of adducts C(70)[S(2)Fe(2)(CO)(6)](n)() where n = 1-4. HPLC analyses show one, four, and three isomers for the adducts, respectively.     

Hydrogen elimination from a hydroxycyclopentadienyl ruthenium(II) hydride: study of hydrogen activation in a ligand-metal bifunctional hydrogenation catalyst

At high temperatures in toluene, [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)]Ru(CO)(2)H (3) undergoes hydrogen elimination in the presence of PPh(3) to produce the ruthenium phosphine complex [2,5-Ph(2)-3,4-Tol(2)-(eta(4)-C(4)CO)]Ru(PPh(3))(CO)(2) (6). In the absence of alcohols, the lack of RuH/OD exchange, a rate law first order in Ru and zero order in phosphine, and kinetic deuterium isotope effects all point to a mechanism involving irreversible formation of a transient dihydrogen ruthenium complex B, loss of H(2) to give unsaturated ruthenium complex A, and trapping by PPh(3) to give 6. DFT calculations showed that a mechanism involving direct transfer of a hydrogen from the CpOH group to form B had too high a barrier to be considered. DFT calculations also indicated that an alcohol or the CpOH group of 3 could provide a low energy pathway for formation of B. PGSE NMR measurements established that 3 is a hydrogen-bonded dimer in toluene, and the first-order kinetics indicate that two molecules of 3 are also involved in the transition state for hydrogen transfer to form B, which is the rate-limiting step. In the presence of ethanol, hydrogen loss from 3 is accelerated and RuD/OH exchange occurs 250 times faster than in its absence. Calculations indicate that the transition state for dihydrogen complex formation involves an ethanol bridge between the acidic CpOH and hydridic RuH of 3; the alcohol facilitates proton transfer and accelerates the reversible formation of dihydrogen complex B. In the presence of EtOH, the rate-limiting step shifts to the loss of hydrogen from B.     

Synthesis and Structure of a Ruthenium（Ⅱ）-dithiocarbamate Complex [RuH（CO）（PPh_3）_2（4-ClPhNHCS_2）]·C_6H_（14）

The title complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817(2),b = 14.3889(2),c = 15.2136(2) ,α = 71.018(1),β = 74.911(1),γ = 85.146(1)°,V = 2214.86(6) 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ(MoKα) = 0.616 mm-1,F(000) = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I > 2σ(I) and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824(8),2.3495(8) and 1.71(2),respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.     

Acceptor (CF3)PCPH pincer reactivity with (PPh3)3Ir(CO)H

The syntheses of Ir(I) and Ir(III) complexes incorporating the electron-withdrawing pincer ligand (1,3-C(6)H(4)(CH(2)P(CF(3))(2))(2)) ((CF(3))PCPH) with (PPh(3))(3)Ir(CO)H and subsequent chemistry are reported. Under ambient conditions, reaction of 1 equiv. (CF(3))PCPH with (PPh(3))(3)Ir(CO)H gave the mono-bridged complex [Ir(CO)(PPh(3))(2)(H)](2)(μ-(CF(3))PCPH) (1). Reaction of (PPh(3))(3)Ir(CO)H with excess (CF(3))PCPH and MeI gave the doubly-bridged complex [Ir(CO)(PPh(3))(H)](2)(μ-(CF(3))PCPH)(2) (2), whereas the tetrameric oligomer [Ir(CO)(PPh(3))(H)](4)(μ-(CF(3))PCPH)(4) (2-sq) was obtained from a 1:1 ligand:metal mixture in benzene in the presence of excess MeI. At higher temperatures (165 °C) the reaction of (CF(3))PCPH with (PPh(3))(3)Ir(CO)H afforded the 5-coordinate Ir(I) complex ((CF(3))PCP)Ir(CO)(PPh(3)) (3). Complex 3 shows mild catalytic activity for the decarbonylation of 2-naphthaldehyde in refluxing diglyme (162 °C).     

Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases

A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.