4-(S)-[2-(N-甲基)吗啉基 ]-5-(R )-(l-薄荷烷氧基 )-丁内酯结构分析

N－甲基吗啉对5－（l－薄荷烷氧基）－2（5H）－呋喃酮的光催化不对称共轭加生成了4－（S）－[2－（N－甲基）吗啉基]－5－（R）－(l－薄荷烷氧基）－丁内酯,在四氢呋喃（THF）对比实验、参比物^13CNMR对照及不同溶剂^13CNMR测定的基础上,该新化合物的结构用高分辨率的子核磁共振谱、碳核磁共振谱、质谱、红外光谱及元素分析、旋光度等数据进行了确证。     

Synthesis and Crystal Structure of (L)_2W(CO)_4·CH_3COCH_3 (L=1-Phenacylimidazole)

1 INTRODUCTION Due to their variability in binding modes, five- membered heterocyclic ligands such as pyrazole[1] and 1,2,4-triazole[2] have been drawn much attention. Consequently, there are numerous reports on their derivatives. Imidazoles resemble pyrazoles, and they are isomeric five-membered heterocyclic molecules containing two nitrogen atoms. Furthermore, imida- zole is also a ring component of adenine and purine, one of the most versatile binding sites in biological systems, so th…     

Me_3NO存在下Ir_4(CO)_(11)L(L=CO,PPh_3)的CO取代反应动力学研究

刊用FT-IR和UV技术跟踪反应进程,研究了在Me_3NO存在下Ir_4(CO)_(12)和Ir_4(CO)_(11)PPh_3分别在CHCl_3—C_2H_5OH和CHCl_3溶剂中取代羰基反应的动力学与机理。结果表明反应遵循二级速率定律:r=k_2[Me_3NO][配合物]。该速率方程与缔合机理相一致。将Ir_4(CO)_(11)L和Os_3(CO)_(11)L(L=CO,PPh_3)体系的动力学结果相比较,着重讨论了桥基因素对反应活性的影响。     

Theoretical studies on Ru(fppz)_2(CO)L (L=N-heterocyclic ligand):Electronic structure,absorption,phosphorescence,and solvatochromism

A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to explore their electronic structures, absorption, and emissions as well as the solvatochrom-ism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1-3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is con-tributed by π*(L). Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing elec-tron-withdrawing group on ligand L will induce remarkable solvatochromism.     

[Ho_2(phen)_4(H_2O)_4(OH)_2](phen)_2(NO_3)_4的合成、晶体结构及磁性

在甲醇与水的混合溶剂中,经浓硝酸硝化的Ho_2O_3与1,10-邻菲啰啉反应形 成氢氧根桥联的双核钬配合物[Ho_2(phen)_4(H_2O)_4(OH)_2] (phen)_2(NO_3)_4 （phen = 1,10-邻菲啰啉）。单晶X射线衍射晶体结构测定表明晶体属三斜晶系, P1-bar (no. 2)空间群,晶胞参数a = 1.1241(1) nm, b = 1.1439(1) nm, c = 1. 4058 (1) nm, α = 93.989(7)°, β = 98.173(7)°, γ = 108.19(1)°, V = 1.6874(4) nm~3, Z = 1, D_c = 1.737 g/cm~3, F(000) = 880,7752个独立衍射 点中,5702个可观测点满足F_o~2 ≥ 2σ (F_o~2),R_1 = 0.0499, wR_2 = 0. 858。标题配合物由中心对称的双核[Ho_2(phen)_4(H_2O)_4-(OH)_2]~(4+)配阳离 子,邻菲啰啉phen分子及硝酸根NO_3~-阴离子组成。敏个稀土原子与2个邻菲啰啉 配体,2相水分子和2个氢氧根配位形成配位数为8的[HoN_4O_4]四方反棱柱。配位 多面体通过两氢氧根基团形成共棱的[Ho_2N_8O_6]双四方反棱柱[d(Ho-N) = 0. 2549～0.2565 nm, d(Ho-O_(H_2O) = 0.2356, 0.2366 nm, d(Ho-O_(OH)) = 0. 2223, 0.2240 nm]。通过氢键和芳环堆积作用,配阳离子和邻菲啰啉分子排列形成 平行于（10 1-bar）的两维层结构,NO_3~-阴离子位于层之间。标题配合物为顺磁 物质,在5 ～300K区间内遵循Curie-Weiss定律X_m (T + 4.43) = 14.72 cm~3·K ·mol~(-1)(X_m为每摩尔Ho~(3+)离子磁化率）,其Ho~(3+)离子的室温有效磁矩为 10.76 B. M.,与Ho~(3+)自由离子的磁矩基本相同,表明稀土离子间不存在磁交换 作用。     

Synthesis, Electrochemistry, Fluorescence and ECL of Ru (phen)_2 (dcbpy) (PF_6)_2

HighlyluminescentRu(II).Os(II)andRe(l)metalcomplexesareapromisingclassofelectrochemiluminescent(ECL)materials'.WehavedesignedandsynthesizedRu(phen)=(dcbpy)(PF,)=Thesyntheticrouteisshownasfollows,4,4-dicarboxylicacid-2,2-bipyridine(dcbpy)wassynthesize...     

A Novel （3,4）-Connected Self-penetrating Net, [Cd_3（OABDC）_2（bipy）_2（H_2O）_2]_n

A new luminescent Cd(Ⅱ) compound, [Cd3(OABDC)2(bipy)2(H2O)2]n (1, H3OABDC = 5-oxyacetateisophthalic acid, bipy = 4,4'-bipyridine), has been prepared by the assembly of Cd(Ⅱ) salt with the mixed ligands of H3OABDC and 4,4'-bipy under hydrothermal conditions. The crystal structure is of monoclinic, space group P2/n with a = 13.6730(5), b = 10.1265(3), c = 15.9752(4) , β = 103.061(3)o, V = 2154.70(11) 3, C40H34Cd3N4O18, Mr = 1195.94, Z = 2, Dc = 1.843 g/cm3, F(000) = 1180, μ = 1.549 mm-1, the final R = 0.0409 and wR = 0.1291 for 2746 observed reflections (I > 2σ(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a self-penetrating two-dimensional (2D) layered structure. According to topology analysis, this 2D framework can be characterized as a (3,4)-connected (6.72)2 (62.8)2 (73.8.102) net that has never been reported before. Finally, these 2D layers are further linked by intermolecular hydrogen bonds and π…π interactions to form a three-dimensional (3D) supramolecular framework. Moreover, Compound 1 exhibits strong blue photoluminescence at room temperature.     

CRYSTAL STRUCTURE OF Mo_2(u-S)_2(S_2P(OEt)_2)_4

<正> Mr=996.91, triclinic, P1, a=8.773(2), b=9.712(3), c=13.652(1) A; α=69.24(0), β=70.43(3), γ=66.87(l)°; Z=l, Dx=1.699 g/cm 3. Final R=0.053 for 3186 reflections with I≥3a(I). There is an interesting trans influence of μ-s bridge in this binuclear cluster. Mo-Mo distance is 2.752(1) A.     

双膦配合物Ru（OAc）_2（Ph_3P）（dppe）和Ru（OAc）_2（dppe）_2的设计合成、表征和氢化性能

Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）_２和１或２摩尔的双－（二苯基膦）乙烷（ｄｐｐｅ）在回流的甲苯中反应，分别生成双膦配位的Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）（ｄｐｐｅ）和Ｒｕ（ＯＡｃ）_２（ｄｐｐｅ）_２。并进行了元素分析、ＩＲ、ＮＭＲ等谱学表征。在温度－５０至４０℃的范围内，测定了Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）（ｄｐｐｅ）的￣（３１）Ｐ｛￣１Ｈ｝ＮＭＲ谱，讨论了配合物中膦配体的配位状态。在反应温度３０至９０℃、氢压１．０至５．０ＭＰａ的条件下，考察了两个配合物均相催化丙烯酸和苯乙烯的氢化性能。结果表明，题示的两个配合物是催化丙烯酸和苯乙烯氢化的有效催化剂。     

中性配合物Cr(acac)_3、mer-和fac-[Cr(bza)_3]的光学拆分

本文用新方法合成了Cr(bza)_3,改进了其mer-、fac-异构体的分离方法;增大了Cr(acac)_3的化学拆分量(1.5g)。试制了DBT(二苯甲酰-d-酒石酸)吸附型手性固定相(CSP),并成功地用于色谱拆分标题配合物的对映体,mer-[Cr(bza)_3]的部分拆分是首次发现的,其他配合物的拆分结果均优于文献方法。根据mer-[Cr(bza)_3)拆分流出液前、后组分的CD光谱,指定了其对映体绝对构型。还讨论了DBT吸附型CSP的拆分效能和色谱特性。     

CRYSTAL STRUCTURE OF W_4(μ_(3-)S)_4[S_2P(OEt)_2]_6

<正> W4S4 [S2P (OEt)2]6, Mr= 1974. 94, triclinic, P1, a = 14. 063 (5) , b = 16. 289(4), c= 13. 377(3) A ,α=92. 06 (2), β=95. 24(3), γ= 73. 06(2)°, V= 2919(3)A3,Z=2,DC=2. 18g/cm3, Moka radiation,λ =0. 71069A ,μ = 90. 64cm-1, F(000) = 1764,R=0. 053 and Rw = 0. 069 for 5422 reflections with I≥3σ(I).The title compound is comprised of a cubane-like cluster core [W4S4] in which every W atom is coordinated by six S atoms to form a distorted octahedron.     

SYNTHESES AND CRYSTAL STRUCTURE OF [Et_4N]{Mo(CO)_5L}(L=I~-,SPh~-)

<正> Crystal of [Et4N][Mo(CO)5I](1) (Mr = 493. 15) is tetragonal with space group P4/n, a =b==9. 374(2) ,c=10. 545(2)(?), V=926. 5(?)3, Z = 2, F(000) = 480, Dc=1. 77g/cm3and μ = 23. 6cm-1. R = 0. 040, Rw = 0.043 for 374 observed reflections. Crystal of [Et4N][Mb(CO)5(SPh)] (2) is orthorhombic ith space group Pbam, a= 15. 230(3), b = 18. 389(10), c=8. 172(3)(?), V=2288. 6 (?)3, Z = 4, Dc=1. 38gcm3, μ = 6.7cm-1.R = 0. 043, Rw = 0. 042 for 1621 observed reflections. Complexes 1 and 2 possess the same geometry. The Mo atom is octahe-drally coordinated with obvious trans drrdct, all the Mo -C bond lengths are shorter obviously and the C - O bond are longer than those of Mo(CO)6.     

Li(THF)2(μ-Cl)2YCl2(THF)2的晶体和分子结构

配合物Li(THF)_2(μ-Cl)_2YCl_2(THF)_2,M=526.10,结构已由X射线衍射法测定,空间群C_2/c,a=21.333(5),b=10.371(10),c=22.559(4)(?),β=90.87(1)°,V=4990.4(?)~3,Z=8,μ(Cu K_a)=75.378cm~(-1),F(000)=2160,R=0.073。     

Synthesis,Crystal Structure and Thermal Properties of Zn(NH_3)_3(AFT)_2

A new coordination compound of Zn(NH_3)_3(AFT)_2(1,ZnC_6H_(13)N_(17)O_2,AFT =4-amino-3-(5-tetrazolate)-furazan)was synthesized and characterized by elemental analysis and FT-IR spectrum.Its crystal structure was determined by X-ray single-crystal diffraction.This crystal belongs to the orthorhombic system,space group Pnma with a = 18.680(3),b = 6.9438(11),c =12.268(2)A,μ= 1.592 mm-1,V= 1591.3(4)A3,M,= 420.72,Dc=1.756 g·cm-3,Z= 4,F(000)= 860,the final R = 0.0480 and wR = 0.1262 for the observed reflections with I2σ(Ⅰ).The zinc(Ⅱ)ion is five-coordinated by N atoms from two AFT"ligands and three NH3 molecules.The thermal decomposition mechanism of compound 1 was tested by differential scanning calorimetry(DSC)and thermogravimetry-derivative thermogravimetry(TG-DTG)methods.The DSC curve exhibits two endothermic and one exothermic processes.In addition,the non-isothermal kinetics parameters were calculated by using the Kissinger s method and Ozawa-Doyle's method.Besides,the entropy of activation(ΔS≠),enthalpy of activation(ΔH≠),free energy of activation(ΔG≠)and impact sensitivity(IS)was also obtained.     

Spectroelectrochemical studies of [Mo(dtc)_4][Eu(dtc)_4] and [Mo(dtc)_4][Er(dtc)_4]

Redox and spectroscopic properties of the eight-coordination complexes of molybdenum and the rare-earth elements Eu or Er with N,N-diethyldithiocarbamate (dtc) were characterised by cyclic voltamrnetry and UV-visible absorption spectra.The complex cation [Mo(dtc)4]+ is more stable than the complex anions [Eu(dtc)4]-and [Er(dtc)4]-in redox processes,and possesses good redox reversibility.The electron transfer number,formal standard electrode potential in the redox process for the complex cation and its diffusion coefficients were obtained by in aitu spectroelectro-chemistry.     

{[Sm_2(Gly)_6(H_2O)_4](ClO_4)_6(H_2O)_5}_n的合成和晶体结构

本文合成了标题配合物,对其红外光谱进行了研究.测定了配合物的晶体结构,结果表明,晶体属三斜晶系,P1空间群,单胞参数:α=11.549(2)(?),b=14.122(3)(?),c=15.654(?),α=97.01(2)°,β=102.70(2)°,γ=105.43(2)°,V=2355.94(0.87)(?)~3,Z=2.晶体结构是采用Patterson法和差值Fourier合成解出.经全矩阵最小二乘法修正,最后偏差因子R=0.0337,R_w=0.0364.晶体中甘氨酸与Sm原子的结合方式有三种:第一种甘氨酸的羧基离子以螯合桥式与Sm原子配位;第二种甘氨酸以羧基桥式与同一单元的两个Sm原子配位;第三种甘氨酸以酸基桥式连结两个相邻单元中的相邻Sm原子而形成一维无限长链结构.此外,每个Sm原子还与两个水分子成键,其配位数为9.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

{Cd(dmt)_2(Hchdc)_2(H_2O)_2}_n配合物的合成与表征

通过水热合成的方法,以1,4-环己烷二羧酸、2,4-二氨基-6-甲基三嗪和CdCl_2·2.5H_2O为原料合成了一种单核的化合物{Cd(dmt)_2(Hchdc)_2(H_2O)_2}_n(dmt=2,4-diamino-6-methyl-triazine,H2chdc=1,4-cyclohexanedicarboxylic acid),并进行了IR和X射线单晶衍射(常温)的分析.结果表明,该化合物属于P2/c空间群,单斜晶系,晶胞参数:a=1.330 26(11)nm,b=0.541 47(4)nm,c=2.415 54(16)nm,β=115.751(3)°,V=1.567 1(2)nm~3,Z=2,Dc=1.570g/cm~3,F(000)=764,R1=0.035 2,wR2=0.092 7.该化合物中,中心金属离子Cd(II)与氧相连形成六配位构型,并通过4种不同的氢键作用最终形成了三维的堆积结构.     

分子导体(PyH)[Ni(dmit)_2]_2的合成、结构与导电性

合成了一种新的导电分子晶体(PyH)[Ni(dmit)_2]_2 (Py = pyridine, dmit = (C_3S_5)~(2-) = 4,5-dimercapto-1,3-dithiole-2-thione)，用元素分析、红 外光谱对其进行了表征，并用四圆X射线衍射方法确定了结构，该晶体属于三斜晶 系，P-1空间群；晶胞参数为: a = 0.59227(4) nm，b = 0.82279(6) nm, c = 1. 67535(9) nm, α = 90.233(5)°, β = 92.107(5)°, γ = 104.654(6)°; V = 0.78925(9) nm~3, Z = 1. (PyH)[Ni(dmit)_2]_2晶体中，导电组元[Ni(dmit)_2] ~(-0.5) 沿b轴方向形成具有二聚体结构的柱状堆积，在(001)面形成以肩并肩分子 间的S…S强相互作用为特征的二维导电层，这种二维导电层上的室温电导率为0. 13 Ω~(-1)·cm~(-1)，在c轴方向，(PyH)~+与[Ni(dmit)_2]~(-0.5)之间除库仑作 用外，还存在N-H…S，C-H…S氢键相互作用。单晶(001)面上变温电阻的测定结果 表明，在90 K到室温的温度范围内，(PyH)[Ni(dmit)_2]_2具有半导体导电行为， 导电激活能为0.15 eV。     

(QuinH)_3〔Mo(i-mnt)_4〕的晶体和分子结构

(QuinH)_3 [Mo(i-mnt)_4]为黑色柱状晶体(式中Qui=喹啉 难溶于水,在空气中很稳定。晶体属单斜晶系,空间群Cc,晶胞参数:a=10.688(16),b=31.545(5),c=14.682(26),B=109.28(14)°;ρobs=1.50克/厘米~3,Z=4(ρcalc=1.489克/厘米~3)。晶体在CAD-4衍射仪上,用Mo-Kα射线,θ-2θ扫描方式,在1°<θ<23°范围内收集了4275个独立衍射点。晶体结构用Patterson函数法和Fourier合数法解出,经全矩阵最小二乘方修正,偏离因子R=0.075。结构分析结果说明Mo原子与四个双齿螯合配位基的八个硫原子形成近似于D_(2d)对称性的十二面体结构。