2-(5-甲基-1,3,4-噻二唑)-硫乙酸镍(Ⅱ)配合物的合成和晶体结构

本文合成了2个镍配合物[Ni(mtyaa)2(H2O)4]·4(H2O)(1)和[Ni(4,4′-bipy)2(mtyaa)2(H2O)2]·2H2O(2)(Hmtyaa=2-(5-甲基-1,3,4-噻二唑)-硫乙酸;4,4′-bipy=4,4′-联吡啶),用X-射线单晶衍射仪测定了配合物的单晶结构,并对它进行了元素分析、红外光谱、热重和粉末X-射线衍射等表征。配合物1和2的晶体分别属于三斜晶系和单斜晶系,空间群分别为P1和P21/n。X-射线单晶结构分析表明配合物1和2中镍原子均采取六配位扭曲的八面体配位模式。在配合物1中配位水和游离水分子与羧基氧之间的氢键作用将单分子结构连成三维网状结构。配合物2中配位水和游离水分子与羧基氧以及配体中的氮原子之间的氢键作用将链连接成二维层状结构。     

小分子配体诱导合成N,N-二苄基二硫代氨基甲酸镉(Ⅱ)配合物及晶体结构

4,4'-联吡啶与二苄基二硫代氨基甲酸镉配合物[Cd(DBTC)2]2(1)反应得到加合物[Cd(DBTC)2(4,4'-bipy)](2)(DBTC=N,N-二苄基二硫代氨基甲酸),通过晶体结构分析及红外光谱等研究其结构与性质.结果表明:引入小分子配体会破坏[Cd(DBTC)2]2(1)的二聚结构,加入吡啶则得到单核的吡啶加合物[Cd(DBTC)2py](3),而引入4,4'-联吡啶后其结构变为新型的一维链状结构的配位聚合物2,这种结构在二硫代氨基甲酸金属配合物中少见报道.也比较了不同配体如吡啶及4,4'-联吡啶对Cd(Ⅱ)及Zn(Ⅱ)配合物结构的影响.     

镍、钴超分子配合物的合成、晶体结构及理论计算（英文）

通过水热法合成了2个新的金属-有机超分子配合物[Ni(eoba)(phen)(H_2O)_2]·0.58H_2O(1)和[Co(eoba)(phen)]2·H_2O(2)(H_2boba=4,4′-(乙烷-1,2-二氧基)-二苯甲酸,phen=菲咯啉),并对其进行了元素分析、红外光谱、热重和X射线单晶衍射测定。配合物1和2是同构的,每个配合物都是六配位的,菲咯啉分子上的2个氮原子、4,4′-(乙烷-1,2-二氧基)-二苯甲酸配体上的2个氧原子和2个配位水分子与金属配位。此外,还用高斯09程序PBE0/LANL2DZ方法对配合物1进行了自然键轨道(NBO)分析,计算结果表明配位原子与Ni原子之间存在着共价作用。     

基于非贵金属镍的金属有机大环的光解水放氢性能

将具有NN(氮氮)双齿配位点的席夫碱配体L2(L2=1,4-苯二-2′-吡啶腙)与镍构筑得到一例[2+2]型金属有机大环[Ni_2(L_2)_2(CH_3CN)_4](ClO_4)_4·4CH_3CN(2),并将其用于可见光条件下的光解水产氢研究。该非贵金属光催化体系由催化剂、光敏剂(荧光素,Fl)和电子牺牲剂(三乙胺)三部分组成。相比于具有相同配位环境的单核配合物[Ni(L_1)_2(CH_3CN)_2](ClO_4)2(1,L1=3-甲酰基苯-2′-吡啶腙),金属有机大环2作为催化剂具有较高的光催化活性,其产氢TON值可以达到3 100 molH_2·molcat-1,归因于荧光素分子可能与金属有机大环2形成超分子配合物,提高了光致电子转移效率。     

4,4′-联吡啶、吡嗪和咪唑桥联铜、镍配合物的合成和磁性

合成了六个含氮杂环桥联配合物:[Ni(salal)_2(4,4’-bipy)]_n、[Ni(Et-dtp)_2(4,4’-bipy]_n、[Cu-(acac)_2(4,4’-bipy)]_n、[Cu(TTA)_2(pyz)]_n、[Cu(TTA)(Im)]_n和[Cu(Im)_2]_n,用元素分析、IR、MS、ESR和热重分析对它们的结构和性质作了表征.吡嗪配合物的晶体结构显示,吡嗪配位于拉伸八面体的轴向位置,桥联Cu(TTA)_2形成一维无限链状结构.变温磁化率表明,4,4’-联吡啶和吡嗪配合物的磁性遵从Curie-Weiss定律,分子内没有明显的磁交换作用.咪唑配合物中存在着较强的反铁磁性交换作用,磁交换常数分别为-75和-107cm~(-1).对4,4’-联吡啶、吡嗪和咪唑传递磁交换的性质作了讨论.     

N,N′-乙二水杨酰胺合镍(Ⅱ)酸根的双核镍(Ⅱ)及镍(Ⅱ)-铜(Ⅱ)配合物的合成及性能研究

以N,N′-乙二水杨酰胺合镍酸钠同二价金属离子和2,2-联吡啶(bpy)或1,10菲绕啉(phen)反应制得双核配合物,[Ni(samen)Cu(L)]和[Ni(samen)Ni(L)_2](L=bpy,phen).经元素分析。红外、电子光谱等方法已推定[Ni(samen)]~2-中的Ni(Ⅱ)的配位环境为平面四方型,而被bpy或phen配位的Cu(Ⅱ)和Ni(Ⅱ),分别为平面四方型和畸变八面体构型。 据此,本文指派了配合物的电子光谱,评价了Dq,B,β等配位场参数,并且用配位场理论模型算出了有效磁矩,Ni(Ⅱ)-Cu(Ⅱ)配合物的g_(11),与g_1,结果理论值与实验值相当吻合。     

[M(4,4'bpy)(N_3)_2]_n(4,4'bpy为4,4'-联吡啶, M=Mn(Ⅱ),Ni(Ⅱ),Cu(Ⅱ),Fe(Ⅱ))的合成、表征、晶体结构和磁性研究

报道了一个由μ-1, 3-N3-和4,4′-联吡啶桥联的配合物{Mn(4,4′bpy)(N3)2}n的合成、晶体结构和磁性. 该配合物具有罕见的脚手架状的三维结构, 磁性测量表明配合物具有弱的反铁磁性J(N3-) = -5.74 cm-1, J(4,4′bpy) = -0.72 cm-1. 同时还报道了其衍生物({Ni(4,4′bpy)(N3)2}n, {Cu(4,4′bpy)(N3)2}n, {Fe(4,4′bpy)(N3)2}n)的合成和表征.     

[M(4,4′bpy)(N3)2]n(4,4′bpy为4,4′-联吡啶, M = Mn(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Fe(Ⅱ))的合成、表征、晶体结构和磁性研究

报道了一个由--1, 3-N3-和4,4′-联吡啶桥联的配合物{Mn(4,4′bpy)(N3)2}n的合成、晶体结构和磁性. 该配合物具有罕见的脚手架状的三维结构, 磁性测量表明配合物具有弱的反铁磁性J(N3-) = -5.74 cm-1, J(4,4′bpy) = -0.72 cm-1. 同时还报道了其衍生物({Ni(4,4′bpy)(N3)2}n, {Cu(4,4′bpy)(N3)2}n, {Fe(4,4′bpy)(N3)2}n)的合成和表征.     

铼联吡啶配合物的电喷雾质谱研究

利用电喷雾质谱（ESI-MS）对2，2'-联吡啶-4,4'-二羧酸乙酯与过渡金属铼的 系列配合物[（4,4'-(OOEt)_2-bpy)Re(CO)_3RPF_6] [其中bpy = 2,2'-联吡啶，R = 吡啶、4-甲基吡啶、4-羟基吡啶、4-氨基吡啶、10-（4-甲基吡啶基）吩噻嗪（ py-PTZ）进行分析，研究了配合物及其配体在不同源内CID(in-source collision induced dissociation, in-source CID)的相对稳定性。结果表明，随着源内 CID电压的升高，配合物中的配体R容易脱落并形成稳定的联吡啶三羰配位离子[(4, 4'(COOEt)_2-bpy)Re(CO)_3]~+。配体脱落从易到难的顺序为：吡啶 > 4-甲基吡啶 >-甲基吡啶>4-羟基吡啶>4-氨基吡啶>py-PTZ。     

对乙酰氨基苯甲酸和含氮配体构筑铜、锌配合物的合成、结构及性质研究(英文)

利用对乙酰氨基苯甲酸(HPABA)和邻菲咯啉(phen)、硝酸铜在DMF/CH3OH/H2O溶液中合成了单核铜配合物[Cu(PABA)(phen)(H2O)2]·(NO3)·H2O(1),然后又和4,4′-联吡啶(4,4′-bpy)、硝酸锌在DMF/CH3OH/H2O溶液中获得配位聚合物{[Zn(PABA)2(4,4′-bpy)]·4H2O}n(2)。根据X射线衍射分析结果,配合物1中每个铜离子周围有2个氮原子和3个氧原子与之配位形成畸变的四方锥配位构型,然而在配合物2中,六配位八面体构型的锌离子通过配体4,4′-联吡啶扩展为一维Zigzag型链。分别对这两个配合物的热稳定性和电化学性质进行了研究。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.