含镧金属富勒烯不同溶剂的高温高压提取

将金属原子或离子置于以Ｃ６０、Ｃ８２为代表的富勒烯笼内形成金属富勒烯包合物是目前富勒烯研究的热点课题［１～３］．合成的金属富勒烯常伴随生成较难分离的空心富勒烯,传统的索氏提取法效率又较低,使得金属富勒烯的深入研究受到限制［１,２］．本文采用改进的高温...     

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（…     

γ－氯代丁酸酯的合成研究

γ－氯代丁酸酯的合成研究周龙虎，史达清，戴桂元（徐州师范学院化学系，２２１００９）γ－氯代丁酸醋是重要有机合成试剂，它是用于合成广谱抗菌剂环丙氟哌酸和环丙氟啶酸的中间体环丙胺及新型拟除虫菊醋中间体环丙酸的原料￣［１］。合成γ－氯代丁酸酯常用的方法有￣...     

［60］富勒烯与β－二羰基化合物的［3＋2］环加成反应

［６０］富勒烯与β－二羰基化合物的［３＋２］环加成反应日本化学家报道了一种新的［６０］富勒烯与β－二羰基化合物的［３＋２］环加成反应。反应的通法是在哌啶存在下以氯苯为溶剂，将［６０］富勒烯与β－二羰基化合物于室温搅拌３５小时，得到的产物是二氢呋喃稠合...     

1,2,3-三取代贫电子环丙烷衍生物与甲醇反应的研究

环丙基的化学性质类似于烯键,亲电试剂对环丙基的反应已研究得较多［１－４］．由于带多个吸电子官能基的环丙烷衍生物的合成较为困难,因此,有关亲核试剂对环丙基的反应报道较少．作者通过肿叶立德 １与米氏酸衍生物 ２的反应,简便地合成了一系列 １,２,３一三取代贫电子环丙烷衍生物３［５,６］．并用此方法高立体选择性地合成了一系列二氢呋喃衍生物［７］及γ－丁酸内酯衍生物［８］等．为弄清亲核试剂对贫电子环丙烷衍生物的反应情况,作者对亲核试剂与环丙烷类衍生物化合物３的反应作了研究．本文报道顺－１－苯甲酰基－２－对…     

1,3—偶极环加成反应在杂螺环化合物合成中的应用

氧化腈与４，４－亚甲基－１－甲基哌啶的１，３－偶极环加成反应生成了杂螺［４．５］葵烷化合物，反应具有立体专一性．产物经ＬｉＡｌＨ４还原生成了γ－氨基醇，最后经插入Ｃ－１单元扩环生成了新的杂螺［５．５］十一烷化合物     

3-甲基-3-氧杂丁环甲醇的阳离子型开环聚合

三元和四元环醚具有较大的环张力而易于聚合．Ｖａｎｄｅｎｂｅｒｇ等［１］曾经以（ｉ－Ｂｕ３）Ａｌ／Ｈ２Ｏ为引发剂,使３－甲基－３－（三甲基硅氧甲基）氧杂丁环进行开环聚合反应,合成的聚合物水解后得到线形的聚甲基羟甲基醚．本文以ＢＦ３·ＯＥｔ２为引发剂,对３－甲基－３－氧杂丁环甲醇进行直接引发,实现了开环聚合反应,得到基本线形或轻度支化的聚醚多元醇．１　实验部分１．１　聚合物的合成　聚合装置同文献［１］．所用试剂按文献［１］方法处理．向烧瓶中加入２０ｍＬ的二氯乙烷和０．１ｍｏｌ３－甲基－３－氧杂丁环甲…     

铱(I)苯乙胺Schiff碱络合物催化苯乙酮的不对称氢转移反应

以光学活性的苯乙胺和吡啶－２－甲醛缩合而得到的Ｓｃｈｉｆ碱（ＰＰＥＩ）（ＰＰＥＩ＝２－［［Ｎ－（１－ｐｈｅｎｙｌｅｔｈｙｌ）ｉｍｉｎｏ］ｍｅｔｈｙｌ］ｐｙｒｉｄｉｎｅ或２－［［Ｎ－（１－苯乙基）亚胺］甲基］吡啶）为配体，进而与［Ｉｒ（ＣＯＤ）Ｃｌ］２（ＣＯＤ＝１，５－环辛二烯）反应，合成了８个光学活性铱络合物，考察了它们在异丙醇存在下催化苯乙酮不对称氢转移反应的光学活性，发现［Ｉｒ（ＣＯＤ）（ＰＰＥＩ）Ｉ］具有较好的立体选择性．其光学产率最高可达３５．７％ｅ．ｅ．．     

纳米金刚石球晶的激光溅射产生与透射电镜表征

在高温高压合成金刚石技术日趋成熟的同时，气相沉积（CVD）条件下实现常压金刚石膜的合成已倍受人们的关注．利用脉冲激光溅射石墨，发现可在一定的基底上获得一类具有某些金刚石特征的薄膜，即类金刚石碳膜（DLC）［‘－‘j．这为在常规条件下合成金刚石带来了新的希望．但DLC只具有金刚石的某些特征，而基本上不具备晶体的有序结构［”’j．我们曾报道了在激光液相溅射的产物中观察到众多的碳球D‘，并通过高分辨透射电镜（HREM）、选区衍射（SAED）及其它相关实验，确定了其具有金刚石结构．且实验部分实验所用的激光是Q开关Nd…     

溴代丙酮酸乙酯的新合成法

溴代丙酮酸乙酯的新合成法黄锦霞，徐章煌，方国苏（湖北大学化学系武汉４３００６２）溴代丙酮酸乙酯是一种重要的化学物质，广泛用于医药、农药及天然产物的合成中［１］。它的合成已报道的有三条路线￣［２－４］，这些方法存在的不足之处是：（１）收率均不高（分别为...     

Separation and identification of perchlorinated polycyclic aromatic hydrocarbons by high-performance liquid chromatography and ultraviolet absorption spectroscopy

High-performance liquid chromatography (HPLC) was coupled with ultraviolet absorption spectroscopy (UV) for the simultaneous separation and identification of a series of perchlorinated polycyclic aromatic hydrocarbons, such as perchlorobenzene (C6Cl6), perchloronaphthalene (C10Cl8), perchlorobiphenyl (C12Cl10), perchloroanthracene (C14Cl10), perchlorophenanthrene (C14C10), perchloroacenaphthylene (C12Cl8), perchloropyrene (C16Cl10) and perchlorofluoranthene (C16Cl10). HPLC was performed on an ODS column using methanol-hexane (80:20) as mobile phase at a flow-rate of 1.0 ml/min. UV absorption spectra of the elutes were detected in the region of 210-350 nm.     

Synthesis of carbaalane halogen derivatives

The carbaalane halogen derivatives [(AlX)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (X = F (9), Cl (7), Br (10), I (11)) were prepared in toluene from [(AlH)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (6) and BF(3).OEt(2), BX(3) (X = Br, I), Me(3)SnF, and Me(3)SiX (X = Cl, Br, I), respectively. A partially halogenated product [(AlH)(2)(AlX)(4)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (12) (X = Cl (approximately 40%), Br (approximately 60%)) was obtained from 5 and impure BBr(3). [(AlH)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (5) was converted to [(AlX)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (X = F (13), Cl (14), Br (15), I (16)) using BF(3).OEt(2) and Me(3)SiX (X = Cl, Br, I), respectively. The X-ray single-crystal structures of 11.C(6)H(6), 12.3C(7)H(8), 13.6C(7)H(8), and 15.4C(7)H(8) were determined. Compounds 7 and 9-11 are soluble in benzene/toluene and could be well characterized by NMR spectroscopy and MS (EI) spectrometry. The results demonstrate the facile substitution of the hydridic hydrogen atoms in 5 and 6 by the halides with different reagents.     

Enlargement of globular silver alkynide cluster via core transformation

The multinuclear metal-ligand supramolecular synthon R-C≡C?Ag(n) (R = alkyl, cycloalkyl; n = 3, 4, 5) has been employed to construct two high-nuclearity silver ethynide cluster compounds, [Cl(6)Ag(8)@Ag(30)((t)BuC≡C)(20)(ClO(4))(12)]·Et(2)O (1) and [Cl(6)Ag(8)@Ag(30)(chxC≡C)(20)(ClO(4))(10)](ClO(4))(2)·1.5Et(2)O (chx = cyclohexyl) (2), that bear the same novel Cl(6)Ag(8) central core. The synthesis of 1 made use of [Cl@Ag(14)((t)BuC≡C)(12)]OH as a precursor, and its reaction with AgClO(4) in CH(2)Cl(2) resulted in an increase in nuclearity from 14 to 38. The results presented here strongly suggest that the formation of multinuclear silver ethynide cage complexes 1 and 2 proceeds by a reassembly process in solution that involves transformation of the encapsulated chloride template within a Ag(14) cage into a cationic pseudo-O(h) Cl(6)Ag(8) inner core, leading to the generation of a much enlarged Cl(6)Ag(8)@Ag(30) cluster within a cluster. To our knowledge, this provides the first example of the conversion of a silver cluster into one of higher nuclearity via inner-core transformation.     

Adventures in crystallization. Crystalline salts containing one, two, or even three chemically distinct cations obtained from solutions of [(cyclohexyl isocyanide)(4)Rh(I)]+

By judicious selection of crystallization conditions, it has been possible to obtain the salts of a common building block, [(RNC)4Rh(I)]+, in single-crystal form suitable for X-ray diffraction. Salts that contain a single type of cation include deep green [(C6H11NC)12Rh(I)3](SbF6)3, deep green [(C6H11NC)12Rh(I)3](AsF6)3, and straw yellow [(C6H11NC)8Rh(II)2Cl2](BF4)2 (in addition to the previously isolated trimeric deep green [(i-PrNC)12RhI3]Cl3 x 4.5 H2O, monomeric, [(C6H11NC)4 Rh(I)](BPh4), and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2 x 0.5C6H6 x 2H2O). Ordered crystals of [(C6H11NC)12Rh(I)3](SbF6)3 contain linear Rh3 units, while those of [(C6H11NC)12Rh(I)3](AsF6)3 show disorder which is consistent with the presence of linear or bent Rh3 units. The formation of green [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)12Rh(I)3]Cl6, and brown [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)8Rh(I)2][(C6H11NC)4RhI]Cl6 x 16H2O x 3C6H6 along with unidentified red-brown cubes from an air-exposed solution of [(C6H11NC)4Rh(I)]Cl is reported. As their formulas indicate, green [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)12Rh(I)3]Cl6, and brown [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)8Rh(I)2][(C6H11NC)8Rh(I)]Cl6 x 16H2O x 3C6H6 contain two or three chemically distinct cations, respectively, but again are built from a common precursor, [(C6H11NC)4Rh(I)]+.     

Probing the ruthenium-cumulene bonding interaction: synthesis and spectroscopic studies of vinylidene- and allenylidene-ruthenium complexes supported by tetradentate macrocyclic tertiary amine and comparisons with diphosphine analogues of ruthenium and osmium

The synthesis and spectroscopic properties of trans-[Cl(16-TMC)Ru[double bond]C[double bond]CHR]PF(6) (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, R = C(6)H(4)X-4, X = H (1), Cl (2), Me (3), OMe (4); R = CHPh(2) (5)), trans-[Cl(16-TMC)Ru[double bond]C[double bond]C[double bond]C(C(6)H(4)X-4)(2)]PF(6) (X = H (6), Cl (7), Me (8), OMe (9)), and trans-[Cl(dppm)(2)M[double bond]C[double bond]C[double bond]C(C(6)H(4)X-4)(2)]PF(6) (M = Ru, X = H (10), Cl (11), Me (12); M = Os, X = H (13), Cl (14), Me (15)) are described. The crystal structures of 1, 5, 6, and 8 show that the Ru-C(alpha) and C(alpha)-C(beta) distances of the allenylidene complexes fall between those of the vinylidene and acetylide relatives. Two reversible redox couples are observed by cyclic voltammetry for 6-9, with E(1/2) values ranging from -1.19 to -1.42 and 0.49 to 0.70 V vs Cp(2)Fe(+/0), and they are both 0.2-0.3 and 0.1-0.2 V more reducing than those for 10-12 and 13-15, respectively. The UV-vis spectra of the vinylidene complexes 1-4 are dominated by intense high-energy bands at lambda(max) < or = 310 nm (epsilon(max) > or = 10(4) dm(3) mol(-1) cm(-1)), while weak absorptions at lambda(max) > or = 400 nm (epsilon(max) < or = 10(2) dm(3) mol(-1) cm(-1)) are tentatively assigned to d-d transitions. The resonance Raman spectrum of 5 contains a nominal nu(C[double bond]C) stretch mode of the vinylidene ligand at 1629 cm(-1). The electronic absorption spectra of the allenylidene complexes 6-9 exhibit an intense absorption at lambda(max) = 479-513 nm (epsilon(max) = (2-3) x 10(4) dm(3) mol(-1) cm(-1)). Similar electronic absorption bands have been found for 10-12, but the lowest energy dipole-allowed transition is blue-shifted by 1530-1830 cm(-1) for the Os analogues 13-15. Ab initio calculations have been performed on the ground state of trans-[Cl(NH(3))(4)Ru[double bond]C[double bond]C[double bond]CPh(2)](+) at the MP2 level, and imply that the HOMO is not localized purely on the metal center or allenylidene ligand. The absorption band of 6 at lambda(max) = 479 nm has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal nu(C[double bond]C[double bond]C) stretch mode accounts for ca. 50% of the total vibrational reorganization energy, indicating that this absorption band is strongly coupled to the allenylidene moiety. The excited-state reorganization of the allenylidene ligand is accompanied by rearrangement of the Ru[double bond]C and Ru[bond]N (of 16-TMC) fragments, which supports the existence of bonding interaction between the metal and C[double bond]C[double bond]C unit in the electronic excited state.     

3-邻氯苯基-3-(5,5二甲基-3-羟基-2-环己烯-1-酮-2-基)丙酸乙酯的合成和晶体结构

标题化合物C19H23O4Cl（4）是由邻氯苯甲醛（1）与5，5-二甲基-1，3-环己二酮（2）、2，2-二甲基-1，3-二氧六环-4，6-二酮（3）在乙醇中反应而得。结构通过单晶X-射线衍射分析确定，其晶体属于单斜晶系，空间群晶体结构用直接法解出，使用全矩阵最小二乘法对原子参数进行修正，最后的偏离因子R＝0．034，Rw＝0．042。在晶体结构中存在一个共轭的烯醇结构。单晶X-射线分析表明；平面1（C（1）～C（6）、Cl）和平面2（C（8）～C（10）、C（12）、C（13））之间的两面角为97．11°，原子C（7）呈变形的四面体构型。     

Mononuclear Schiff base boron halides: synthesis, characterization, and dealkylation of trimethyl phosphate

A series of mononuclear boron halides of the type LBX(2) [LH = N-phenyl-3,5-di-tert-butylsalicylaldimine, X = Cl (2), Br (3)] and LBX [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (7), Br (8); LH2 = N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (9), Br (10); and LH2 = N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (11), Br (12)] were synthesized from their borate precursors LB(OMe)2 (1) (LH = N-phenyl-3,5-di-tert-butylsalicylaldimine) and LB(OMe) [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine (4), N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine (5), N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine (6)]. The boron halide compounds were air and moisture sensitive, and upon hydrolysis, compound 7 resulted in the oxo-bridged compound 13 that contained two seven-membered boron heterocycles. The boron halide compounds dealkylated trimethyl phosphate in stoichiometric reactions to produce methyl halide and unidentified phosphate materials. Compounds 8 and 12 were found to be the most effective dealkylating agents. On reaction with tert-butyl diphenyl phosphinate, compound 8 produced a unique boron phosphinate compound LB(O)OPPh2 (14) containing a terminal phosphinate group. Compounds 1-14 were characterized by 1H, 13C, 11B, 31P NMR, IR, MS, EA, and MP. Compounds 5, 6, and 11-14 also were characterized by single-crystal X-ray diffraction.     

Cyclodiphosphazanes with hemilabile ponytails: synthesis, transition metal chemistry (Ru(II), Rh(I), Pd(II), Pt(II)), and crystal and molecular structures of mononuclear (Pd(II), Rh(I)) and bi- and tetranuclear rhodium(I) complexes

Cyclodiphosphazanes having hemilabile ponytails such as cis-[(t)()BuNP(OC(6)H(4)OMe-o)](2) (2), cis-[(t)()BuNP(OCH(2)CH(2)OMe)](2) (3), cis-[(t)BuNP(OCH(2)CH(2)SMe)](2) (4), and cis-[(t)BuNP(OCH(2)CH(2)NMe(2))](2) (5) were synthesized by reacting cis-[(t)()BuNPCl](2) (1) with corresponding nucleophiles. The reaction of 2 with [M(COD)Cl(2)] afforded cis-[MCl(2)(2)(2)] derivatives (M = Pd (6), Pt (7)), whereas, with [Pd(NCPh)(2)Cl(2)], trans-[MCl(2)(2)(2)] (8) was obtained. The reaction of 2 with [Pd(PEt(3))Cl(2)](2), [{Ru(eta(6)-p-cymene)Cl(2)](2), and [M(COD)Cl](2) (M = Rh, Ir) afforded mononuclear complexes of Pd(II) (9), Ru(II) (11), Rh(I) (12), and Ir(I) (13) irrespective of the stoichiometry of the reactants and the reaction condition. In the above complexes the cyclodiphosphazane acts as a monodentate ligand. The reaction of 2 with [PdCl(eta(3)-C(3)H(5))](2) afforded binuclear complex [(PdCl(eta(3)-C(3)H(5)))(2){((t)BuNP(OC(6)H(4)OMe-o))(2)-kappaP}] (10). The reaction of ligand 3 with [Rh(CO)(2)Cl](2) in 1:1 ratio in CH(3)CN under reflux condition afforded tetranuclear rhodium(I) metallamacrocycle (14), whereas the ligands 4 and 5 afforded bischelated binuclear complexes 15 and 16, respectively. The crystal structures of 8, 9, 12, 14, and 16 are reported.     

Magnetooptical and structural investigations of five dimeric cobalt(II) complexes mimicking metalloenzyme active sites

Four novel cobalt(II) complexes mimicking metalloenzyme active sites, novel C(14)H(22)Cl(12)Co(2)O(13)·2C(3)H(8)O (1), C(28)H(36)Cl(24)Co(4)O(28)·4C(4)H(8)O(2) (2), C(16)H(22)Cl(12)Co(2)O(13)·C(2)HCl(3)O(2) (3), C(16)H(22)Cl(12)Co(2)O(13) (4), and one known C(40)H(78)Cl(8)Co(2)O(17) (5) are composed of the same core of two high-spin cobalt(II) centers triply bridged by water and two trichloroacetato (1-4) or two pivalate (5) groups but differ in terminal ligands. The crystal structures of new compounds 1-4 belong to the space groups P ?1, P2(1)/c, P ?1, and Pbcn, respectively. All five investigated complexes contain Co atoms in distorted octahedral coordination. The complexes were characterized by magnetic susceptibility and magnetization measurements and by variable-temperature variable-field magnetic circular dichroism spectroscopy. Experimental data were analyzed in the frame of the theoretical model, which includes an unquenched orbital moment of the Co(II) ions. All investigated compounds are antiferromagnetically coupled with exchange constants in the range -1.5 to -2.1 cm(-1). However, there is a significant difference between the crystal-field-splitting parameters.     

Single-molecule magnets: a new family of Mn(12) clusters of formula [Mn(12)O(8)X(4)(O(2)CPh)(8)L(6)

The reaction of (NBu(n)(4))[Mn(8)O(6)Cl(6)(O(2)CPh)(7)(H(2)O)(2)] (1) with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the Mn(II)(2)Mn(III)(10) title compounds [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hmp)(6)] (2) and [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hep)(6)] (3), respectively, with X = Cl. Subsequent reaction of 3 with HBr affords the Br(-) analogue [Mn(12)O(8)Br(4)(O(2)CPh)(8)(hep)(6)] (4). Complexes 2.2Et(2)O.4CH(2)Cl(2), 3.7CH(2)Cl(2), and 4.2Et(2)O.1.4CH(2)Cl(2) crystallize in the triclinic space group P1, monoclinic space group C2/c, and tetragonal space group I4(1)/a, respectively. Complexes 2 and 3 represent a new structural type, possessing isomeric [Mn(III)(10)Mn(II)(2)O(16)Cl(2)] cores but with differing peripheral ligation. Complex 4 is essentially isostructural with 3. A magnetochemical investigation of complex 2 reveals an S = 6 or 7 ground state and frequency-dependent out-of-phase signals in ac susceptibility studies that establish it as a new class of single-molecule magnet. These signals occur at temperatures higher than those observed for all previously reported single-molecule magnets that are not derived from [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(x)]. A detailed investigation of forms of complex 2 with different solvation levels reveals that the magnetic properties of 2 are extremely sensitive to the latter, emphasizing the importance to the single-molecule magnet properties of interstitial solvent molecules in the samples. In contrast, complexes 3 and 4 are low-spin molecules with an S = 0 ground state.