含1,2二取代的苯并咪唑配体的Zn(Ⅱ)络合物上化学固定CO2转化为环状碳酸酯

合成了一种新的Zn(Ⅱ)配合物ZnCl2(L1)2] (1) (L1为 2-(2-噻吩)-1-(2-噻吩甲基)-1H-苯并咪唑),并采用NMR和IR光谱、元素分析、ESI-HRMS光谱测定和热重分析等对它进行了表征,其分子结构也由单晶X射线衍射确定.络合物1含有单核四面体Zn(Ⅱ)单元,即所谓的锁定的几何结构,这源自分子中存在弱的分子间S···π和π-π配体间相互作用.通过简易的合成路线即可制得苯并咪唑配体及其与Zn(Ⅱ)配合物.采用CO2与环氧化物耦合生成环状碳酸酯反应考察了1的催化活性,以及反应条件的影响.该配合物在无溶剂条件下可高效催化多种环氧化物的转化,具有较好的转化率,TONs和TOFs.     

含1,2二取代的苯并咪唑配体的Zn(Ⅱ)络合物上化学固定CO_2转化为环状碳酸酯（英文）

合成了一种新的Zn(Ⅱ)配合物ZnCl_2(L1)_2](1)(L1为2-(2-噻吩)-1-(2-噻吩甲基)-1H-苯并咪唑),并采用NMR和IR光谱、元素分析、ESI-HRMS光谱测定和热重分析等对它进行了表征,其分子结构也由单晶X射线衍射确定.络合物1含有单核四面体Zn(Ⅱ)单元,即所谓的锁定的几何结构,这源自分子中存在弱的分子间S···p和p-p配体间相互作用.通过简易的合成路线即可制得苯并咪唑配体及其与Zn(Ⅱ)配合物.采用CO_2与环氧化物耦合生成环状碳酸酯反应考察了1的催化活性,以及反应条件的影响.该配合物在无溶剂条件下可高效催化多种环氧化物的转化,具有较好的转化率,TONs和TOFs.     

羰基铁-硫醇-三乙胺反应体系的研究, μ-酰基与μ-烯基铁硫配合物的合成系脱羰反应动力学

本文由反式巴豆酰氯与活性中间物[(μ-CO)(μ-R1S)Fe2(CO)6]ˉEt3N^+反应, 合成了两个新的μ-酰基铁硫配合物(μ-R1S)(μ-CH5CH=CHCO)Fe2(CO)6(R1=Et, Bu^t)和三个新的μ-烯基铁硫配合物(μ-R1S)(μ-CH3CH=CH)Fe2(CO)6(R1=Et, Bu^+, CH2=CHCH2), 此外还研究了μ-酰基配合物脱羰生成μ-烯基配合物的反应动力学, 证明为一级反应, 并求得在一定条件下的速率常数和半衰期。     

α-酯甲基硫桥羰基铁配合物(μ-RS)[μ-EtO<(O)CH2S]-Fe2(CO)6的合成及构象分析

通过μ-S2Fe2(CO)6的S-S键被Grignard试剂的还原断裂反应及中间物(μ-RS)(μ-XMgS)Fe2(CO)6(2)对氯代乙酸乙酯的亲核取代反应,合成了一系列铁硫原子簇配合物(μ-RS)[μ-EtOC(O)CH2S]Fe2(CO)6(1).1也可由2经三氟醋酸酸解及中月物(μ-RS)(μ-HS)Fe2(CO)6(3)在三乙胺存在下与氯代乙酸乙酯缩合制得.然而前法较后法既操作简便又原料便宜易得.构象分析表明,各配合物一般为ae.ee和ea三种或其中构象体以一定比例存在的混和物.     

羰基铁-硫醇-三乙胺反应体系的研究, μ-酰基与μ-烯基铁硫配合物的合成系脱羰反应动力学

本文由反式巴豆酰氯与活性中间物[(μ-CO)(μ-R1S)Fe2(CO)6]ˉEt3N^+反应, 合成了两个新的μ-酰基铁硫配合物(μ-R1S)(μ-CH5CH=CHCO)Fe2(CO)6(R1=Et, Bu^t)和三个新的μ-烯基铁硫配合物(μ-R1S)(μ-CH3CH=CH)Fe2(CO)6(R1=Et, Bu^+, CH2=CHCH2), 此外还研究了μ-酰基配合物脱羰生成μ-烯基配合物的反应动力学, 证明为一级反应, 并求得在一定条件下的速率常数和半衰期。     

配合物Ni(Pybox) (SCN)2(CH3OH)的合成、表征与晶体结构

本文合成了含N原子的三齿配体2,6-吡啶二噁唑啉(Pybox),由Pybox与NiCl2·6H2O和KSCN在甲醇溶液中反应制得标题配合物Ni(Pybox)(SCN)2(CH3OH),并进行了元素分析、红外光谱、电子光谱、X-射线衍射等表征.结果表明:此配合物属单斜晶系,空间群为P2(1)/n,晶体学参数为:a=7.9...     

双簇核铁硫配合物[(μ-RS)Fe2(CO)6]2(μ-S-S-μ)的合成

本文报导由μ-S2F2(CO)6及格氏试剂形成的活泼配合物(1), 可在磺酰氯SO2Cl2的作用下, 发生氧化偶联反应生成由S-S键相连的双簇核配合物(2), 本文对所得配合物(2)的反应性能进行了研究。     

抗衡阴离子PF6-调控的1,3-丙二胺缩邻香兰素镧(Ⅲ)配合物的合成和晶体结构

通过柔性配体1,3-丙二胺缩邻香兰素(H2L)与和La(NO3)3.6H2O反应,合成了1个由2个H2L桥连的双核稀土配合物[La2(NO3)6(H2L)2].CH2Cl2(1),该配合物与(NH4)(PF6)继续反应生成了1个由2个NO3-离子桥连的双核配合物[La2(NO3)2(H2L)4](PF6)4.4H2O.2CH2Cl2(2),X-射线单晶衍射分析确定了2个配合物的晶体结构。配合物1和2为结构完全不同的2个双核结构,因抗衡阴离子PF6-有去阴离子的作用,配合物1中的NO3-离子被配体取代,导致配合物1的结构翻转,形成了1个新颖的双核结构2。     

N, N′-二吡啶基-3-亚甲基-1, 2-乙二胺-稀土硝酸盐配合物的合成与表征

在乙腈溶液中合成了N,N′-二吡啶基-3-亚甲基-1,2-乙二胺(L)的稀土硝酸盐系列配合物.利用元素分析、 红外光谱和差热-热重分析等手段对所合成的配合物进行了表征,结果表明合成的配合物都符合稀土金属离子与配体为1∶1的化学计量比,其组成可表示为[RE(NO3)3L]·nH2O [RELa(Ⅲ),Nd(Ⅲ),Eu(Ⅲ),Tb(Ⅲ),Er(Ⅲ),n2.5,1.5,1].另外,初步研究了其中Eu(Ⅲ)和Tb(Ⅲ)配合物在室温固体状态下的荧光性质,结果显示这两个配合物表现出相应的Eu(Ⅲ)和Tb(Ⅲ)离子的特征发射.     

一个具有杂金属链和蜂巢状纳米孔道结构的三维配位聚合物的合成与表征

在溶剂热条件下,用预先合成的5-羟甲基间苯二甲酸(H_2HIA)与Zn2+及K+反应构建出1个具有三维开放框架结构的配位聚合物[Zn_(0.5)K_(0.5)(HIA)(H_2O)]·x Guest(1).在配合物1中,Zn~(2+),K~+与H_2HIA构建出了无限长的杂金属链和具有亲水表面的蜂巢状纳米孔道.粉末X射线衍射和热失重分析结果表明,配合物1为纯相,330℃后有机体开始分解.此外,对配合物1的荧光性质也进行了研究.     

Synthesis of 2-thioxo-3-benzothiazolineacetonitrile and related products

Attempts to thermally rearrange 2-benzothiazolylthioacetonitrile ( 1) to the titled compound 8 failed. The reaction of 3-chloromethyl-2-benzothiazolinethione with potassium cyanide in dimethylformamide (DMF) or dimethylsulfoxide (DMSO) at 25-30° afforded 8 in 98% yield. Whereas replacing the DMF or DMSO solvent with acetone furnished the unexpected sulfide 9 in 92% yield. Substituting 3-chloromethyl-2-benzoxazoline-thione as the electrophile in the same reaction gave the sulfide 10 in 95% yield. Possible mechanisms and supporting nmr data are discussed.     

1-氯-3-硝基-2-丁烯与2-硝基丙烷钠盐的SRN1反应

本文研究了1-氯-3-硝基-2-丁烯与2-硝基丙烷钠盐的SRN1反应, 结果表明这种开链状纯脂肪族烯丙基型化合物发生了不重排的SRN1反应.     

Reactions of metal iodides as a simple route to heterometallics: synthesis, structural transformations, thermal and luminescent properties of novel hybrid iodoargentate derivatives templated by [YL8]3+ or [YL7]3+ cations (L = DMF or DMSO)

A 1 : 3 molar reaction of YI3 and AgI in dimethylformamide (DMF) in the presence of NH4I afforded [Y(DMF)8][Ag3(mu3-I)(mu-I)3I2] (1) with good yield, whereas the similar reaction in dimethylsulfoxide (DMSO) gave complexes [Y(DMSO)8][Ag2(mu-I)3I2] (2) and/or [Y(DMSO)8]2[Ag4(mu3-I)2(mu-I)4I2][I]2 (3), depending on the reaction and crystallization conditions. These discrete heterometallic hybrid compounds 1-3 undergo solid- and solution-state transformations via condensation of iodoargentate anions. So in the confined and solvent-free environment of paratone, crystals of 1 transformed into a 1D zig-zag structure [Y(DMF)8]3+[Ag6(mu4-I)2(mu3-I)2(mu-I)5]1infinity(3-) (4), whereas those of 2 were first converted into 3 and finally into [Y(DMSO)7]4[Ag4(mu3-I)4I4]3 (5). In solution phase, re-crystalization of 1 or 2 from DMSO-toluene gave 3 as an exclusive species, whereas reaction of 1 with 3 equiv of AgI in DMF afforded 4 with good yield. Alternatively, 4 could also be synthesized with excellent yield from a 1 : 6 molar reaction of YI3 and AgI. The above transformations suggest that, for a given metal-organic cation, an iodometallate cluster with higher nuclearity is thermodynamically more stable. Single crystal X-ray structures are reported for all the compounds and a mechanism for the structural transformation of 2 to 3 is proposed. In addition, spectroscopic, thermo-gravimetric and luminescent properties of the complexes 1, 3 and 4, which were obtained exclusively and in pure form, are also described.     

二元混合溶剂的NMR弛豫研究

本文测定了纯CH3OD, DMSO-d6中^2D和DMF中^1^4N的弛豫时间. 参照文献所列核四极矩偶合常数, 按公式计算它们的液体分子取向相关时间, 参照Hertz等的假设, 认为在混合溶剂中各组分的核四极矩偶合常数基本不变, 与纯质相同, 并计算了各组分分子在各个混合溶剂中的取向相关时间, 从而初步讨论了混合溶剂中各组分分子间的相互作用.     

Donor-Acceptor Complexes in Copolymerization. XXVI. Effect of Solvent,Temperature, and Complexing Agent on the Polymerization of Comonomer Charge Transfer Complexes

The copolymerization of styrene with methyl methacrylate (S/MMA = 4/1) or acrylonitrile (S/AN = 1/1) in the presence of ethylaluminum sesquichloride (EASC) yields 1/1 copolymer in toluene or chlorobenzene. In chloroform the S-MMA-EASC polymerization yields 60/40 copolymer while the S-AN-EASC polymerization yields 1/1 copolymer. In the presence of EASC, styrene-α-chloroacrylonitrile yields 1/1 copolymer (DMF or DMSO), S-AN yields 1/1 copolymer (DMSO) or radical copolymer (DMF), S-MMA yields radical copolymer (DMF or DMSO), α-methylstyrene-AN yields radical copolymer (DMSO) or traces of copolymer (DMF), and α-MS-methacrylo-nitrile yields traces of copolymer (DMSO) or no copolymer (DMF). When zinc chloride is used as complexing agent in DMF or DMSO, none of the monomer pairs undergoes polymerization. However, radical catalyzed polymerization of isoprene-AN-ZnCl₂ in DMF yields 1/1 alternating copolymer. The copolymerization of S/MMA in the presence of EASC yields 1/1 alternating copolymer up to 100°C, while the copolymerization of S/AN deviates from 1/1 alternating copolymer above 50°C. The copolymerization of S/MMA deviates from 1/1 copolymer at MMA/EASC mole ratios above 20 while the copolymerization of S/AN deviates from 1/1 copolymer at MMA/EASC ratios above 50.     

Kinetics and reactivity of substituted anilines with 2‐chloro‐5‐nitropyridine in dimethyl sulfoxide and dimethyl formamide

The kinetics of the reaction of substituted anilines with 2‐chloro‐5‐nitropyridine were studied in dimethyl sulfonide (DMSO) and dimethyl formamide (DMF) at different amine concentrations and temperatures in the range 45–60°C. In both solvents the reaction was not a base‐catalyzed one. A plot of ΔH^# versus ΔS^# for the reaction in DMSO and DMF gave good straight lines with isokinetic temperatures 128°C and 105°C, respectively. Good linear relationships were obtained from the plots of log k₁ against σ° values at all temperatures with negative ρ values (?1.63 to ?1.28 in DMSO) and (?1.26 to ?0.90 in DMF). © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 645–650, 2002     

氟烷基化和氟烷氧基化的研究 23: 锌单电子转移引发全氟烷基碘与吡咯的反应

在二甲亚砜或二甲基甲酰胺中, 锌能迅速引发全氟烷基碘(1)与吡咯的反应, 生成2-氟烷基吡咯(3); 在二氧六环中, 主要生成全氟烷基碘的偶合产物5; 在乙腈、二乙二醇二甲醚或苯等溶剂中, 则同时生成3和5, 反应能被二硝基苯阻止. 加入二烯丙基醚能得到氟烷基取代的四氢呋喃衍生物. 反应可能经锌单电子转移引发的自由基机理. 对溶剂效应作了讨论.     

六硝基六氮杂异伍兹烷与二甲基甲酰胺分子加合物的制备、 性能及晶体结构

六硝基六氮杂异伍兹烷(HNIW)可与二甲基甲酰胺(DMF)形成稳定的分子加合物(两者分子比为1:2)。首次报道了该加合物的晶体结构、晶体学数据和结构参数。该加合物为无色透明片状晶体,属三斜晶系,空间群Pi。在该加合物中,HNIW与DMF分子以范德华力结合,彼此间不存在氨键或偶极作用。     

Effect of polar aprotic solvents on the trimerization of phenyl isocyanate by organometallic catalysts

Studies of the trimerization of phenyl isocyanate by organometallic catalysts in the presence of various solvents have shown that dipolar aprotic solvents, such as DMSO and DMF, even in small amounts enhance greatly the rate of reaction. In accordance with their mode of action and of the effect of DMSO or DMF, the catalysts could be divided into three groups. Group I comprises tributyltin oxide, Ti(OBu)₄ and Zr(OBu)₄, which give a fast addition to the isocyanate. Maximum increase in rate was observed at DMSO:PhNCO = 1:1 due to the formation of a 1:1 charge transfer complex between them. Group 2 comprises naphthenates of Pb.Zr and Co which form complexes with the isocyanate, the reaction being much faster with the C.T. complex of DMSO and PhNCO: maximum increase in rate was observed at low DMSO concentrations, about the same as that of the catalyst. Group 3 comprises nucleophiles such as the amine catalysts, where the enhancement in rate was not great, due to the same mode of nucleophilic interaction of the catalyst and DMSO or DMF with the isocyanate.     

X-ray structural studies on microscopic mixing in binary mixtures of dimethyl sulphoxide with acetonitrile and N,N-dimethylformamide

The liquid structures of binary acetonitrile (AN)–dimethyl sulphoxide (DMSO) and N,N-dimethylformamide (DMF)–DMSO mixtures were investigated by the X-ray scattering method. Comparison of the X-ray scattering data of AN–DMSO liquid mixtures with those of neat AN and DMSO revealed that the intermolecular AN–DMSO interactions are practically not detected; that is, the X-ray scattering data of the liquid mixtures are well reproduced by summing up those of neat AN and DMSO weighted by their mole fractions. The same applies for DMF–DMSO mixtures. Thus, each component solvent molecule independently forms self-assembled clusters in the liquid mixtures, the structures of which are the same as those in the neat liquids. The clusters are mixed to form macroscopically homogeneous liquid mixtures. The thermodynamic quantities on mixing process for the AN–DMSO, DMF–DMSO and AN–DMF systems in the literature are well elucidated on the basis of the microscopic structure of the liquid mixtures.