蝎型钒氧苯甲酸配合物的合成、结构及量化计算

设计合成了两种以聚吡唑硼酸盐、苯甲酸为配体的钒氧配合物VO[HB(pz)3](pzH)(C6H5COO)(1)和VO[HB(3,5-Me2pz)3](3,5-Me2pzH)(C6H5COO)(2)((HB(pz)3: 聚吡唑硼酸钠盐; pzH: 吡唑; HB(3,5-Me2pz)3: 聚甲基吡唑硼酸钠盐; 3,5-Me2pzH: 3,5-二甲基吡唑). 通过元素分析、红外光谱和X射线单晶衍射方法对配合物进行了表征. 并结合从头计算结果进一步分析了配合物的稳定性及分子中配键的共价特征. 分析结果表明, 配合物2的稳定性大于配合物1, 中心钒原子周围的价键类型都属于共价键范畴, 键序分析结果与晶体结构测定的键长结果是一致的.     

蝎型钒氧配合物的合成、结构及量子化学研究

设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析.     

Synthesis, structure, luminescence properties, quantum chemistry and cytotoxic effects of two vanadium(IV) complexes with polypyrazolylborates, HB(pz)3VO(acac) and HB(3,5-Me2pz)3VO(acac)·CH3CN (pz = pyrazole)

The reaction of VO(acac)₂ (acac = acetylacetonate) with NaHB(pz)₃ (pz = pyrazole) or NaHB(3,5-Me₂pz)₃ in methanol gave vanadium(IV) complexes HB(pz)₃VO(acac) (1) or HB(3,5-Me₂pz)₃VO(acac)·CH₃CN (2), respectively. The complexes 1 and 2 were characterized by elemental analysis, IR, UV-vis, NMR and X-ray diffraction crystallography methods. Complex 1 crystallizes in space group P2₁/c, a = 7.641(2) Å, b = 17.008(4) Å, c = 13.362(2) Å; β = 92.092(17)°, V = 1735.5(7) ų, Z = 4. Complex 2 crystallizes in space group P2₁/c, a = 17.410(13) Å, b = 8.076(16) Å, c = 19.300(13) Å; β = 101.75(5)°, V = 2657(6) ų, Z = 4. X-ray structure analyses have shown that the complexes 1 and 2 are monomeric with a similar coordination environment of the vanadium atom. Luminescence properties and cytotoxic effects of the complexes are discussed. On CBRH-7919 cells, the complexes 1 and 2 caused a slight stimulation of growth at low doses (1–10 μM) and a significant cytotoxic effect at higher doses (100–1000 μM). The electronic structure and the bonding characters of the two complexes were analyzed with ab initio calculations. Original Russian Text Copyright ? 2006 by Y. H. Xing, Z. Sun, W. Zou, J. Song, K. Aoki, and M. F. Ge __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 5, pp. 924–932, September–October, 2006.     

含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学

设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.     

蝎型钒氧配合物Tp*VO(OOCHCCHCOOCH3)(pz*H)和Tp*VO(DMSO)(NCS)的合成、结构及量子化学研究

本文在室温条件下,甲醇体系中,设计并首次合成了2种蝎型半夹心钒氧配合物Tp*VO(OOCHCCHCOOCH3)(pz*H)(1)和Tp*VO(DMSO)(NCS)(2)(Tp*=三聚3,5-二甲基吡唑硼酸根),通过元素分析、红外光谱对配合物进行了表征,利用X-射线单晶衍射方法对晶体结构进行了测定,并结合从头计算结果进一步分析了配合物的稳定性及分子中配键的共价特征。分析结果表明,配合物1和2的稳定性相近,且中心钒原子周围的价键类型都属于共价键范畴,键序分析结果与晶体结构测定的键长结果是一致的。     

取代基对吡啶双亚胺铁、钴乙烯聚合催化剂的影响

合成了一系列对位取代的2，6－二亚胺吡啶的铁、钴配合物(Ar = 2,6-Me₂C₆H₃, M = Fe: 3a, M = Co: 4a; Ar = 2,4,6-Me₃C₆H₂, M = Fe: 3b, M = Co: 4b; Ar = 2,6-Me₂-4-BrC₆H₂, M = Fe: 3c, M = Co: 4c; Ar = 2,6-Me₂-4-ClC₆H₂, M = Fe: 3d, M = Co: 4d; Ar = 2,4-Me₂-6-BrC₆H₂, M = Fe: 3e, M = Co: 4e; Ar = 2,4-Me₂-6-ClC₆H₂, M = Fe: 3f, M = Co: 4f)，并以改性甲基铝氧烷（MMAO）作为助催化剂研究了其乙烯聚合行为。吡啶双亚氨配体上取代基的位置和电子效应对催化活性和聚合物性质有很大影响。     

三齿配体酰(氧)钒配合物的晶体结构研究——Ⅰ.双聚{1-(2,4-戊二酮-(3-硝基苯甲酰)-单腙-2-乙氧基合氧钒(Ⅳ)}和双聚{1-(2,4-戊二酮-(3-硝基苯甲酰)-单腙-2-甲氧基合氧钒(Ⅳ)的晶体结构

以二乙酰丙酮氧钒VO(Acac)_2与间硝基苯甲酰肼m-NO_2PhCONHNH_2分别在乙醇和甲醇中反应,得[VO(C_(12)H_(12)N_3O_4)(C_2H_5O)]_2(Ⅰ)和[VO(C_(12)H_(12)N_3O_4)(CH_3O)]_2(Ⅱ)两种晶体。晶体(Ⅰ)属空间群P(?),晶胞参数a=8.123(2),b=10.409(5),c=10.822(4),α=65.78(3)°,β=85.50(3)°,r=89.04(3)°。晶体(Ⅱ)属空间群P2_1/a,a=7.745(2),b=19.164(5),c=10.787(4),β=107.87(2)°。两个晶体均具有共同的结构特征:通过缩合形成的三齿配体占据四个赤道配位位置中的三个,男一个赤道配位位置由醇氧基RO~-所补充而RO~-中的氧原子又兼作桥氧向另一个钒原子的第六位配位,从而导致文献中未报道过的新型双核钒配合物的形成。     

配合物VO[(C15H12N2O4)(OC2H5)]的合成晶体结构和氧化还原性质

含有ONO给体原子的N-邻甲氧基苯甲酰基水杨酰肼配体与[VO(acac)2]在乙醇中反应得到钒(V)酰配合物VO[(C15H12N2O4)(OC2H5)].标题化合物晶体属三斜晶系,空间群Pī,晶胞参数:a＝0.894 11(5)nm,b＝1.006 3(2)nm,c＝1.039 2(2)nm,α＝110.171(7)°,β＝95.219(3)°,γ＝93.822(2)°;V＝0.869 2(2)nm3,Z＝2,R1＝0.051 3,wR＝0.153 2.研究结果表明:钒原子具有扭曲的四方锥配位构型,钒酰氧原子处在锥顶位置,配体的3个给体原子与溶剂分子形成锥底平面.     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.     

以3,5-二硝基苯甲酸和吡唑为配体的Ni(Ⅱ),Co(Ⅱ)配合物的合成与晶体结构

以3,5-二硝基苯甲酸(3,5-Hdnbc)和吡唑(pz)为配体与Co2+和Ni 2+反应,得到了2个新的配合物[Co(3,5-dnbc)2(pz)2(H2O)2](1)和[Ni(3,5-dnbc)2(pz)4](2).用元素分析、红外光谱对其进行了表征,并用单晶X-射线衍射测定了配合物的晶体结构;配合物1和2均为单核分子,配合物1通过分子内和分子间氢键形成三维网络超分子结构,而配合物2中只存在分子内氢键.     

Syntheses of Cationic, Six-Coordinate Cadmium(II) Complexes Containing Tris(pyrazolyl)methane Ligands. Influence of Charge on Cadmium-113 NMR Chemical Shifts

Treating a thf (thf = tetrahydrofuran) suspension of Cd(acac)(2) (acac = acetylacetonate) with 2 equiv of HBF(4).Et(2)O results in the immediate formation of [Cd(2)(thf)(5)](BF(4))(4) (1). Crystallization of this complex from thf/CH(2)Cl(2) yields [Cd(thf)(4)](BF(4))(2) (2), a complex characterized in the solid state by X-ray crystallography. Crystal data: monoclinic, P2(1)/n, a = 7.784(2) ?, b = 10.408(2) ?, c = 14.632(7) ?, beta = 94.64(3) degrees, V = 1181.5(6) ?(3), Z = 2, R = 0.0484. The geometry about the cadmium is octahedral with a square planar arrangement of the thf ligands and a fluorine from each (BF(4))(-) occupying the remaining two octahedral sites. Reactions of [Cd(2)(thf)(5)](BF(4))(4) with either HC(3,5-Me(2)pz)(3) or HC(3-Phpz)(3) yield the dicationic, homoleptic compounds {[HC(3,5-Me(2)pz)(3)](2)Cd}(BF(4))(2) (3) and {[HC(3-Phpz)(3)](2)Cd}(BF(4))(2) (4) (pz = 1-pyrazolyl). The solid state structure of 3 has been determined by X-ray crystallography. Crystal data: rhombohedral, R&thremacr;, a = 12.236(8) ?, c = 22.69(3) ?, V = 2924(4) ?(3), Z = 3, R = 0.0548. The cadmium is bonded to the six nitrogen donor atoms in a trigonally distorted octahedral arrangement. Four monocationic, mixed ligand tris(pyrazolyl)methane-tris(pyrazolyl)borate complexes {[HC(3,5-Me(2)pz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (5), {[HC(3,5-Me(2)pz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (6), {[HC(3-Phpz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (7), and {[HC(3-Phpz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (8) are prepared by appropriate conproportionation reactions of 3or 4 with equimolar amounts of the appropriate homoleptic neutral tris(pyrazolyl)borate complexes [HB(3,5-Me(2)pz)(3)](2)Cd or [HB(3-Phpz)(3)](2)Cd. Solution (113)Cd NMR studies on complexes 3-8 demonstrate that the chemical shifts of the new cationic, tris(pyrazolyl)methane complexes are very similar to the neutral tris(pyrazolyl)borate complexes that contain similar substitution of the pyrazolyl rings.     

Mononuclear and binuclear sandwich copper(II) complexes with poly(pyrazolyl)borate ligands: syntheses, structures and properties

A series of Cu(II) complexes Cu(2)[micro-pz](2)[HB(pz)(3)](2) (1), Cu[H(2)B(pz)(2)](2) (2), Cu[HB(pz)(3)](2) (3), Cu[HB(pz(Me2))(3)](2) (4), Cu[B(pz)(4)](2) (5) (pz=pyrazole), have been synthesized and characterized by elemental analysis, IR, UV-vis, X-ray diffraction, thermal analysis and theoretical analysis. The IR spectra give the Cu-N vibration modes at 322, 366, 344, 387, and 380 cm(-1) in complexes 1-5, respectively. The UV spectra show all the complexes have same UV absorption at 232 nm; there is another band at 332 nm for complexes 1, 2 and 4, while for complexes 3 and 5, the bands are at 272 and 308 nm, respectively. Complex 1 has a binuclear structure in which two pyrazole ligands bridge two Cu-Tp units. In 2-5, the Cu(II) centers are coordinated with dihydrobis(pyrazolyl)borate (Bp), hydrotris(pyrazolyl)borate (Tp), hydrotris(3,5-Me2pyrazolyl)borate (Tp'), tetrakis(pyrazolyl)borate (Tkp) respectively to form a mononuclear structure. The results of thermal analysis for complexes 1-5 are discussed too.     

Potassium S2N-heteroscorpionates: structure and iridaboratrane formation

The potassium salts of the new S(2)N-heteroscorpionate ligand hydrobis(methimazolyl)(3,5-dimethylpyrazolyl)borate [HB(mt)(2)(pz(3,5-Me))](-) and its known analogue hydrobis(methimazolyl)(pyrazolyl)borate [HB(mt)(2)(pz)](-) (prepared from KTp' or KTp and methimazole, Hmt), and the adduct KTp·Hmt have polymeric structures in the solid state (the first a ladder and the other two chains). The iridaboratranes [IrHLL'{B(mt)(2)X}] (X = pz(3,5-Me) or pz), prepared from the heteroscorpionate anion and [{Ir(cod)(μ-Cl)}(2)] (LL' = cod), subsequent carbonylation [LL' = (CO)(2)] and then reaction with phosphine [LL' = (CO)(PR(3)), R = Ph or Cy], have a pendant pyrazolyl ring and a bicyclo-[3.3.0] cage formed by an S(2)-bound B(mt)(2) fragment. The binuclear species [(cod)HIr{μ-B(mt)(3)}IrCl(cod)], the only isolated product of the reaction of KTm with [{Ir(cod)(μ-Cl)}(2)], also has an S(2)-bound iridaboratrane unit but with the third mt ring linked to square planar iridium(I).     

Insulin-like model complexes: Synthesis,spectra characterization and crystal structure of two novel oxovanadium complexes with poly(pyrazolyl)borate ligands VO(HB(pz)3)(H2B(pz)2) and VO(B(pz)4)2

Two new oxovanadium (IV) complexes VO(HB(pz)₃)(H₂B(pz)₂) (1) and VO(B(pz)₄)₂ (2) have been obtained by the reaction of oxovanadium sulfate with the corresponding ligands KHB(pz)₃, KH₂B(pz)₂ and KB(pz)₄, respectively. The two complexes were characterized by elemental analyses, IR, UV–Vis and X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group, Pca2₁. Complex 2 crystallizes in the orthorhombic space group, Pna2₁. In both complexes, five nitrogen atoms and one oxygen atom coordinate to the vanadium atom, forming a distorted octahedral geometry (VON₅). In addition, related spectra characterization, hydrogen-binding properties, structural configuration and quantum chemistry calculations are also discussed.     

Synthesis and catalytic properties of molybdenum(VI) complexes with tris(3,5-dimethyl-1-pyrazolyl)methane

The complex [MoO(2)Cl{HC(3,5-Me(2)pz)(3)}]BF(4) (1) (HC(3,5-Me(2)pz)(3) = tris(3,5-dimethyl-1-pyrazolyl)methane) has been prepared and examined as a catalyst for epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (TBHP) as the oxidant. For reaction of cis-cyclooctene, epoxycyclooctane is obtained quantitatively within 5 h when water is rigorously excluded from the reaction mixture. Increasing amounts of water in the reaction mixture lead to lower activities (without affecting product selectivity) and transformation of 1 into the trioxidomolybdenum(VI) complex [{HC(3,5-Me(2)pz)(3)}MoO(3)] (4). Complex 4 was isolated as a microcrystalline solid by refluxing a suspension of 1 in water. The powder X-ray diffraction pattern of 4 can be indexed in the orthorhombic Pnma system, with a = 16.7349(5) ?, b = 13.6380(4) ?, and c = 7.8513(3) ?. Treatment of 1 in dichloromethane with excess TBHP led to isolation of the symmetrical [Mo(2)O(4)(μ(2)-O){HC(3,5-Me(2)pz)(3)}(2)](BF(4))(2) (2) and unsymmetrical [Mo(2)O(3)(O(2))(2)(μ(2)-O)(H(2)O){HC(3,5-Me(2)pz)(3)}] (3) oxido-bridged dimers, which were characterized by single-crystal X-ray diffraction. Complex 2 displays the well-known (Mo(2)O(5))(2+) bridging structure where each dioxidomolybdenum(VI) center is coordinated to three N atoms of the organic ligand and one μ(2)-bridging O atom. The unusual complex 3 comprises dioxido and oxidodiperoxo molybdenum(VI) centers linked by a μ(2)-bridging O atom, with the former center being coordinated to the tridentate N-ligand. The dinuclear complexes exhibit a similar catalytic performance to that found for mononuclear 1. For complexes 1 and 2 use of the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate and N-butyl-3-methylpyridinium tetrafluoroborate as solvents allowed the complexes to be completely dissolved, and in each case the catalyst and IL could be recycled and reused without loss of activity.     

Solid-state (67)zn NMR spectroscopy in bioinorganic chemistry. Spectra of four- and six-coordinate zinc pyrazolylborate complexes obtained by management of proton relaxation rates with a paramagnetic dopant

Solid-state (67)Zn NMR spectra of model compounds for metalloproteins, such as [H(2)B(3,5-Me(2)pz)(2)](2)Zn (pz denotes pyrazolyl ring), have been obtained using low temperatures (10 K) to enhance the Boltzmann factor in combination with cross polarization (CP) from (1)H to (67)Zn. Attempts to observe spectra of other model compounds, such as [H(2)B(pz)(2)](2)Zn, were hindered by long relaxation times of the protons. To decrease the proton relaxation times, the high-spin six-coordinate complex [HB(3,4,5-Me(3)pz)(3)](2)Fe has been investigated as a dopant. NMR and EPR measurements have shown that this Fe(II) dopant effectively reduces the (1)H spin lattice relaxation time, T(1), of the zinc samples in the temperature range 5-10 K with minimal perturbations of the (1)H spin lattice relaxation time in the rotating frame, T(1)(rho). Using this methodology, we have determined the (67)Zn NMR parameters of four- and six-coordinate zinc(II) poly(pyrazolyl)borate complexes that are useful models for systems of biological importance. The (67)Zn NMR parameters are contrasted to the corresponding changes in the (113)Cd NMR parameters for the analogous compounds. Further, these investigations have demonstrated that a temperature-dependent phase transition occurs in the neighborhood of 185 K for [HB(3,5-Me(2)pz)(3)](2)Zn; the other poly(pyrazolyl)borate complexes we investigated did not show this temperature-dependent behavior. This conclusion is confirmed by a combination of room-temperature high-field (18.8 T) solid-state (67)Zn NMR spectroscopy and low-temperature X-ray methods. The utilization of paramagnetic dopants should enable low-temperature cross polarization experiments to be performed on a wide variety of nuclides that are important in bioinorganic chemistry, for example, (25)Mg, (43)Ca, and (67)Zn.