二(β-羟亚胺)二氯化钛配合物的合成及催化乙烯聚合

报道了3个β-羟亚胺配体(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂CH(Ph)OH(1a), (2,6-^emPr₂C₆H₃)N＝C·(Ph)CH₂C(Ph)₂OH(1b)和(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(C₁₂H₈)OH(1c)及其二(β-羟亚胺)二氯化钛配合物[(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂CH(Ph)O]₂TiCl₂(2a), [(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(Ph)₂O]₂·TiCl₂(2b)和[(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(C₁₂H₈)O]₂TiCl₂(2c)的合成, 并对其结构进行了表征. 在助催化剂甲基铝氧烷(MAO)作用下, 以化合物2b为主催化剂, 研究了Al/Ti摩尔比、 反应时间、 温度和聚合压力等对乙烯聚合的影响, 发现该催化体系在较宽的反应条件下均可得到很高分子量的聚乙烯, 熔点均在140℃左右. 以化合物2a~2c为主催化剂对乙烯进行催化聚合, 发现在β碳位上取代基的立体位阻对催化剂活性有很大影响. 当化合物2b上引入2个苯基取代基时, 催化剂显示出最佳催化活性.     

新型取代基炔类分子的合成及其与B(C6F5)3的反应

合成了5种不同取代基的炔类化合物Mes2HSiC≡CPh(1,Mes=2,4,6-Me3C6H2)、[tBuC(NAr)2]GeC≡CPh(2,Ar=2,6-iPr2C6H3)、[PhC(NtBu)2]SnC≡CPPh2(3)、[HC(CMe)2(NAr)2]Sn C≡CPPh2(4)和[HC(CMe)2(NAr)2]ZnC≡CPPh2(5),研究了这些化合物与B(C6F5)3的反应.在与B(C6F5)3的反应中,1和2均发生1,1-碳硼化反应生成烯烃化合物(Ph)(Mes2HSi)C=C(C6F5)B(C6F5)2 (6)和{[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7), 7是一种GeⅡ/B松散Lewis酸碱对化合物;3~5则都发生B(C6F5)3与配体金属基的位置交换、进而配体金属基转换键合PPh2的反应,分别生成新颖的分子内双性离子炔烃化合物[PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3 (8)、[HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3(9)、[HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10).文中还讨论了反应机理.     

铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.     

链状三核钼(钨)硫原子簇化合物[M3O2S8]^2^-的合成, 光谱和晶体结构

本文以[NH4]2MOnS4-n(M=Mo, w, n=0-2)为原料, 在酸性和中性条件下, 合成出九个新的三核不对称钼硫和钨硫原子簇状化合物L2[M3O2S8][L=(n-Bu)4N, Ph4P,PyC16H33, (CH3)3NC16H33, Et4N], 用元素分析, 红外光谱, 紫外光谱对簇合物进行了表征, 并测定了其中[(n-Bu)4N]2[Mo3O2S8]和[n-Bu)4N]2[W3O2S8]两个簇合物的晶体结构。本文又一次验证了钼(钨)硫成簇反应是分子内部电子转反应, 并提出了反应历程。     

含膦配体的羰基钼(O)和钨(O)化合物的改进合成,反应及催化活性

MoCl5或WCl6与锌粉及适当的膦配体和CO在常压常温进行反应,合成了含膦配体的炭基钼和钨的化合物(Ph2PR)nM(CO)6-n(M=Mo,W;R=ME,Et,n-Pr,Ph;n=2,3),用该方法也成功地将M(CO)5(M=Mo,W)单元负载到含膦的高分子链上,化合物(Ph2PEt)2Mo(CO)4与HgCl2反应得到含Mo-Hg键的化合物。用(Ph3P)2Mo(CO)4和(Ph3P)2Ni(CO)2二元催化体系,在适当温度和压力下对甲醇羰基化反应进行初步研究,得到了初步研究,得到了醋酸和醋酸甲酯。该催化过程对甲醇的转化率可达92%,对醋酸和醋酸甲酯的选择性可达68%。     

双核Pt(Ⅳ)配合物与Guanosine-5''''-Monophosphate和Glutathione反应的核磁共振光谱研究

合成了一个新型的双核Pt(Ⅳ)配合物{[cis-Pt(NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物1)及相应的 15N标记化合物{[cis-Pt(15NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物15N-1).利用1H NMR和ESMS进行了结构表征,化合物15N-1的2D[1H,15N]HSQC NMR发现,该化合物在水溶液中存在同分异构体.2D[1H,15N]HSQC NMR技术跟踪了化合物15N-1与Guanosine-5'-Monophosphate(5'-GMP)和Glutathione(GSH)的反应.结果显示,5'-GMP能在0.5 h内将化合物1还原,而GSH在6 h以后才能够部分的将化合物1还原.化合物1所表现出来的反应性能将有利于提高其治疗效果和降低毒副作用.     

PhI(OAc)_2参与的β-酮酸酯及β-酮酰胺亲核氟化反应

报道了一种构建含氟的β-酮酸酯及β-酮酰胺的亲核氟化反应.该反应采用Ph I(OAc)_2为氧化剂、3HF·Et3N为氟化试剂,在室温下反应30min高效构建一系列含有季碳中心的含氟化合物.与传统的亲电氟化反应相比,该方法具有无金属参与、反应时间短、反应条件简单、反应收率高等优点.     

铁钼硫原子簇化合物的合成与结构研究 Ⅴ.[MoFe_3S_4]类立方烷簇合物的转化反应和[Et_4N]_3[Mo_2Fe_6S_8(SC_6H_4CH_(3-m))_3Cl_6]的晶体结构

具[MoFe_3S_4]类立方烷结构单元的双类立方烷化合物[Et_4N]_4[Mo_2Fe_7S_8(SR)_(12)](1a,R=Ph;1b,R=tolyl-m)或单类立方烷化合物[MoFe_3S_4(dtcR_2)_5](2a,R=Me;2b,R=Et)与酰氯在乙腈中反应,分别得到不含Fe桥的双类立方烷化合物(Et_4N)_3[Mo_2Fe_6S_8(SR)_3Cl_6](3a,R=Ph;3b,R=tolyl-m)与[MoFe_3S_4]骨架支解后的Fe(dtcR_2)_2Cl(4a,R=Me;4b,R=Et)。说明在相同反应条件下,[MoFe_3S_4]单元在1中比在2中稳定。本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及~1H NMR谱的证实。本文报道3b的单晶结构及3的~1H NMR数据。3b属六方晶系,P6_3/m,a=1.6827(3),c=1.5951(16)nm;V=3.91158nm~3;D_c=1.491g/cm~3;Z=2;F(000)=1780;偏离因子R=0.048。化合物2与酰氯反应产生4,由红外及紫外可见光谱证实。     

Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

The zirconium nitrate complexes (NO₂)[Zr(NO₃)₃(H₂O)₃]₂(NO₃)₃ (1), Cs[Zr(NO₃)₅] ((2), (NH₄)[Zr(NO₃)₅](HNO₃) (3), and (NO₂)_0.23(NO)_0.77[Zr(NO₃)₅] ((4) were prepared by crystallization from nitric acid solutions in the presence of H₂SO₄ or P₂O₅. The complexes were characterized by X-ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO₃)₃(H₂O)₃]⁺ complex cations in which the Zr^IV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the Zr^IV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO₃)₅]^? anions and Cs⁺ or NH₄ ⁺ cations, respectively. In addition, complex 3 contains HNO₃ molecules. Complex 4 differs from (NO₂)[Zr(NO₃)₅] in that three-fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO⁺, resulting in a decrease in the unit cell parameters. In the [Zr(NO₃)₅]^? anion involved in complexes 2–4, the Zr^IV atom is coordinated by five bidentate nitrate groups and has an unusually high coordination number of 10. The coordination polyhedron is a bicapped square antiprism.     

Al(CN)6(3-) and Al(NC)6(3-) trianions

At this time the smallest trianions observed in the gas phase are fluorinated fullerenes and large organic ring systems with attached sulfonic acid groups. Considerably smaller trianions have been predicted to be sufficiently stable for observation in mass spectrometers, but have not yet been detected. Here two isomers of the aluminium cyanide trianion, Al(CN)(6)(3-) and Al(NC)(6)(3-), are studied using ab initio methods. These two isomers are predicted to be electronically stable and to show substantial barriers with respect to dissociation of CN(-) units. Thus, the investigated trianions hit a sweat-spot regarding the possibility of detection, as they are by far more robust with respect to dissociation than alkali halide trianions, while at the same time materials from which these trianions can at least in principle be formed are much more readily available than those needed for producing small covalently bound trianions.     

Hyperfine structures of the 2 (3)Sigma(g) (+), 3 (3)Sigma(g) (+), and 4 (3)Sigma(g) (+) states of Na(2)

The hyperfine structures of the 2 (3)Sigma(g) (+), 3 (3)Sigma(g) (+), and 4 (3)Sigma(g) (+) states of Na(2) have been resolved with sub-Doppler continuous wave perturbation facilitated optical-optical double resonance spectroscopy via A (1)Sigma(u) (+) approximately b (3)Pi(u) mixed intermediate levels. The hyperfine patterns of these three states are similar. The hyperfine splittings of the low rotational levels are all very close to the case b(betaS) limit. As the rotational quantum number increases, the hyperfine splittings become more complicated and the coupling cases become intermediate between cases b(betaS) and b(beta J) due to spin-rotation interaction. We present a detailed analysis of the hyperfine structures of these three (3)Sigma(g) (+) states, employing both case b(betaS) and b(beta J) coupling basis sets. The results show that the hyperfine splittings of the (3)Sigma(g) (+) states are mainly due to the Fermi-contact interaction. The Fermi contact constants for the two d sigma Rydberg states, the 2 (3)Sigma(g) (+) and 4 (3)Sigma(g) (+), are 245+/-5 MHz and 225+/-5 MHz, respectively, while the Fermi contact constant of the s sigma 3 (3)Sigma(g) (+) Rydberg state is 210+/-5 MHz. The diagonal spin-spin and spin-rotation constants, and nuclear spin-electronic spin dipolar interaction parameters of the 3 (3)Sigma(g) (+) and 4 (3)Sigma(g) (+) states are also obtained.     

Impurity diffusion of (141)Pr in LaMnO(3), LaCoO(3) and LaFeO(3) materials

The impurity diffusion of Pr(3+) in dense polycrystalline LaMnO(3), LaCoO(3) and LaFeO(3) was studied at 1373-1673 K in air in order to investigate cation diffusion in these materials. Cation distribution profiles were measured by secondary-ion mass spectrometry and it was found that penetration profiles of Pr(3+) had two distinct regions with different slopes. The first, shallow region was used to evaluate the bulk diffusion coefficients. The activation energies for bulk diffusion of Pr(3+) in LaMnO(3), LaCoO(3) and LaFeO(3) were 126 +/- 6, 334 +/- 68 and 258 +/- 75 kJ mol(-1), respectively, which are significantly lower than previously predicted by atomistic simulations. The bulk diffusion of Pr(3+) in LaMnO(3) was enhanced compared to LaCoO(3) and LaFeO(3) due to higher concentrations of intrinsic point defects in LaMnO(3), especially La site vacancies. Grain-boundary diffusion coefficients of Pr(3+) in LaCoO(3) and LaFeO(3) materials were evaluated according to the Whipple-Le Claire equation. Activation energies for grain-boundary diffusion of Pr(3+) in LaCoO(3) and LaFeO(3) materials were 264 +/- 41 kJ mol(-1) and 290 +/- 36 kJ mol(-1) respectively. Finally, a correlation between activation energies for cation diffusion in bulk and along grain boundaries in pure and substituted LaBO(3) materials (B = Cr, Fe, Co) is discussed.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).     

LiMn3(SeO3)2(HSeO3)6

The title compound, lithium trimanganese bis­[trioxo­selenate(IV)] hexa­kis[hydrogentrioxoselenate(IV)], is built up from a vertex‐sharing network of distorted Mn^IIIO₆ octa­hedra, SeO₃ and HSeO₃ pyramids and unusual Li(OH)₆ octa­hedra, resulting in a dense three‐dimensional structure. Mn, Li and one Se atom have site symmetries of , , and 3, respectively. An O—H⋯O hydrogen bond helps to establish the crystal packing.     

3He NMR study of (3)He@C(60)H(6) and (3)He@C(70)H(2)(-)(10)

The (3)He NMR of (3)He@C(60)H(6), (3)He@C(70)H(2), (3)He@C(70)H(4), (3)He@C(70)H(8), and (3)He@C(70)H(10) have been investigated. A new, unidentified C(60)H(6) isomer has been found by using (3)He NMR. (3)He@C(70)H(10) shows the most downfield-shifted (3)He NMR resonance among the neutral C(70) derivatives.     

Analysis of the intermolecular interaction between CH(3)OCH(3), CF(3)OCH(3), CF(3)OCF(3), and CH(4): high level ab initio calculations

The intermolecular interaction energies of the CH₃OCH₃? CH₄, CF₃OCH₃? CH₄, and CF₃OCF₃? CH₄ systems were calculated by ab initio molecular orbital method with the electron correlation correction at the second order Møller–Plesset perturbation (MP2) method. The interaction energies of 10 orientations of complexes were calculated for each system. The largest interaction energies calculated for the three systems are ?1.06, ?0.70, and ?0.80 kcal/mol, respectively. The inclusion of electron correlation increases the attraction significantly. It gains the attraction ?1.47, ?1.19, and ?1.27 kcal/mol, respectively. The dispersion interaction is found to be the major source of the attraction in these systems. In the CH₃OCH₃? CH₄ system, the electrostatic interaction (?0.34 kcal/mol) increases the attraction substantially, while the electrostatic energies in the other systems are not large. Fluorine substitution of the ether decreases the electrostatic interaction, and therefore, decreases the attraction. In addition the orientation dependence of the interaction energy is decreased by the substitution. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 1472–1479, 2002