多碘阴离子与双核配合物阳离子的超分子组装

通过多碘阴离子与双核配合物阳离子的超分子组装获得了3个新的化合物并对其进行了X射线结构测定和红外光谱,紫外-可见光谱的表征。它们是[(NiCl(bpy)~2)~2^2^+](I~3^-)~2(I~2)(1),[(MnCl(bpy)~2)~2^2^+](I~3^-)~2(I~2)(2)和[(MnCl(bpy)~2)~2^2^+](I~7^-)~1~/~2(I~5^-)(I~3^-)~1~/~2(I~2)~1~/~2(bpy=2,2'-bipyridine)(3)。晶体学数据：1单斜晶系,空间群C2/c,a=1.37091(3)nm,b=1.67996(3)nm,c=2.20708(5)nm,β=91.6114(12)°,V=5.08106(18)nm^3,Z=4,对4367个可观测反射点R1=0.0674;2单斜晶系,空间群C2/c,a=1.38898(3)nm,b=1.70579(4)nm,c=2.22092(4)nm,β=92.9168(13)°,V=5.25523(19),Z=4,对4485个可观测反射点R1=0.0470;3三斜晶系,空间群P-1,a=1.10793(4)nm,b=1.43488(5)nm,c=1.98724(8)nm,α=100.6352(16)°,β=96.4348(19)°,γ=110.0297(19)°,V=2.86409(18)nm^3,Z=2,对7156个可观测反射点R1=0.0634。这三个化合物中都含有具有分叉形状的双核配合物阳离子[(MCl(bpy)~2)~2]^2^+(M=Mn,Ni),它们通过配体bpy之间的π-π堆垛构成带孔洞的层状结构,在层中由配体bpy围成的孔洞填充了I~2分子或I~3^-阴离子,组装成由I~2分子或I~3^-阴离子穿越的正电性的层。在层和层之间则占据了相互连接的I~2,I~3^-,I~5^-,I~7^-,并与层中的I~2,I~3^-相连,形成复杂的具有无限扩展结构的多碘离子的网络,在网络中,多碘离子构成了直径达纳米的孔道结构。对化合物的红外光谱(4000～50cm^-^1)进行了归属。化合物1和3的紫外-可见漫反射光谱(200～800nm)为无特征的宽吸收带,源于无限扩展结构的多碘离子上的电子离域。     

单、双核镍(II)配合物的晶体结构、光谱和磁性

报道2个具有三足四齿配体,三(2-甲基吡啶)胺(缩写TPA)的单、双核镍(II)配合物。X射线晶体结构分析结果表明,双核镍配合物(1)晶体(C~3~6H~3~6N~8Ni~2Cl~2).11/6(ClO~4).1/6(OH).8/6(H~2O)属三方晶系,空间群为R-3,a=2.8425(4)nm,b=2.8425(4)nm,c=1.4385(5)nm,α=β=90.00ⅲ,γ=120.00ⅲ,Z=18,最终因子R=0.078,Rw=0.078。单核配合物晶体C~2~0H~1~8N~6NiS~2.0.5(H~2O),属三斜晶系,空间群P1,a=0.9467(1)nm,b=1.5566(3)nm,c=1.5913(3)nm,α=73.59(4)ⅲ,β=87.37(3)ⅲ,γ=76.27(2)ⅲ,Z=4,最终因子R=0.0784,Rw=0.238。双核配合物的变温磁化率(4-300K)数据表明,用最小二乘法进行理论拟合(H=-2JS~1.S~2),得出交换积分J=6.72cm^-^1,θ=-0.60cm^-^1,表明双核镍之间为弱的铁磁相互作用,分子间为弱的反铁磁相互作用。     

单、双核镍(II)配合物的晶体结构、光谱和磁性

报道2个具有三足四齿配体,三(2-甲基吡啶)胺(缩写TPA)的单、双核镍(II)配合物。X射线晶体结构分析结果表明,双核镍配合物(1)晶体(C~3~6H~3~6N~8Ni~2Cl~2).11/6(ClO~4).1/6(OH).8/6(H~2O)属三方晶系,空间群为R-3,a=2.8425(4)nm,b=2.8425(4)nm,c=1.4385(5)nm,α=β=90.00ⅲ,γ=120.00ⅲ,Z=18,最终因子R=0.078,Rw=0.078。单核配合物晶体C~2~0H~1~8N~6NiS~2.0.5(H~2O),属三斜晶系,空间群P1,a=0.9467(1)nm,b=1.5566(3)nm,c=1.5913(3)nm,α=73.59(4)ⅲ,β=87.37(3)ⅲ,γ=76.27(2)ⅲ,Z=4,最终因子R=0.0784,Rw=0.238。双核配合物的变温磁化率(4-300K)数据表明,用最小二乘法进行理论拟合(H=-2JS~1.S~2),得出交换积分J=6.72cm^-^1,θ=-0.60cm^-^1,表明双核镍之间为弱的铁磁相互作用,分子间为弱的反铁磁相互作用。     

N-氧化吡啶-2-甲醛衍生物的配合物研究 III: N-氧化吡啶 -2-甲醛缩氨基硫脲的双核铜配合物的晶体结构和电子结构

合成了N-氧化吡啶 -2-甲醛缩氨基硫脲的双核铜配合物。晶体结构的测定表明两Cu原子之间是通过两个单原子氧桥相联, 每个桥联氧原子既处于一个Cu原子为中心的四方锥底面, 又是另一个Cu原子四方锥的锥顶。晶体属单斜晶系, 空间群为Ce, 晶体结构参数为a=16.445,b=13.889,c=12.770A,β=122.82°。根据半经验MO法的计算结果, 指出了红外谱中N-O键和C=N 键特征峰朝不同方向位移的原因, 并对磁偶合常数作了估计。     

N-氧化吡啶-2-甲醛衍生物的配合物研究 III: N-氧化吡啶 -2-甲醛缩氨基硫脲的双核铜配合物的晶体结构和电子结构

合成了N-氧化吡啶 -2-甲醛缩氨基硫脲的双核铜配合物。晶体结构的测定表明两Cu原子之间是通过两个单原子氧桥相联, 每个桥联氧原子既处于一个Cu原子为中心的四方锥底面, 又是另一个Cu原子四方锥的锥顶。晶体属单斜晶系, 空间群为Ce, 晶体结构参数为a=16.445,b=13.889,c=12.770A,β=122.82°。根据半经验MO法的计算结果, 指出了红外谱中N-O键和C=N 键特征峰朝不同方向位移的原因, 并对磁偶合常数作了估计。     

含N,O和S的Schiff碱配体的双核锌配合物的合成与晶体结构

本文合成了具有隔室构造的Schiff碱配体H3L(L^3^-=C11H11N6OS2^3^-), 并对其进行了元素分析, IR, ^1H NMR和MS等项表征。制备了该配体的分别由醋酸根和吡啶分子协配的两种锌的双核配合物, 对后者进行了X射线单晶结构分析。[Zn2L(OH)(py)2](py)2, P21/c, a=0.9195(1), b=2.3334(6), c=1.6111(3)nm,β=93.99(1)°, Z=4。结构用直接法解得, 最终的R=0.066。测定的结果表明,两锌原子间存在酚氧和羟基的两μ2-O-桥, 每个五配位的锌均具有四方锥型的配位构型。     

新型手性双核Salen锰（III）配合物对咪唑、吡啶类客体的分子识别研究

合成并表征了新型手性双核Salen配体1及其锰（III）配合物2（主体2）。用 紫外-可见光谱滴定法研究了主体2与四种咪唑类、四种吡啶类客体在CHCl_3中的分 子识别行为。实验结果表明：对咪唑客体的缔合常数按K（Im） > K (2 - Melm) > K (N-MeIm) > K (EtMelm)顺序递减；吡啶类顺序为K （PyO） > K (4-PhPyO) > K (DMAP) > K(Py)，配位数n值均为2。测定了识别过程的Δ_rH_m，Δ_rS_m， 发现此类反应为放热、熵减小的过程，反应体系中存在焓熵补偿关系。与单核的 Salen锰（III）配合物3（主体3）进行比较，除EtMeIm与3的配位数为1外，其他唑 类客全的配位数均为2。就与客体的缔合能力而言，主体2比3大。用圆二色光谱（ CD）研究了主-客体的分子识别行为。     

新型手性双核Salen锰（III）配合物对咪唑、吡啶类客体的分子识别研究

合成并表征了新型手性双核Salen配体1及其锰（III）配合物2（主体2）。用 紫外-可见光谱滴定法研究了主体2与四种咪唑类、四种吡啶类客体在CHCl_3中的分 子识别行为。实验结果表明：对咪唑客体的缔合常数按K（Im） > K (2 - Melm) > K (N-MeIm) > K (EtMelm)顺序递减；吡啶类顺序为K （PyO） > K (4-PhPyO) > K (DMAP) > K(Py)，配位数n值均为2。测定了识别过程的Δ_rH_m，Δ_rS_m， 发现此类反应为放热、熵减小的过程，反应体系中存在焓熵补偿关系。与单核的 Salen锰（III）配合物3（主体3）进行比较，除EtMeIm与3的配位数为1外，其他唑 类客全的配位数均为2。就与客体的缔合能力而言，主体2比3大。用圆二色光谱（ CD）研究了主-客体的分子识别行为。     

具有生物活性的金属配合物的研究 III: 3-6(二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物的合成, 性质及抗肿瘤活性

合成了十五种新的3,6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物, 其化学式为: [C17H20N2I]3[RE(C6H5O7)2].xH2O(RE=La-Nd, x=5; Sm-Tb, x=4; Dy-Lu, Y,x=3). 利用X射线粉末衍射、热重-差热, 红外光谱、紫外光谱、摩尔电导等对这些配合物进行了表征. 试验表明, 镧配合物对L7712癌细胞DNA合成的抑制率(97.3%)明显高于其前体(C17H20N2I^+.HCOO^-, 72.5%; Na3[La(C6H5O7)2], -16.5%.     

二(2-苯并咪唑亚甲基)胺配合物的合成、晶体结构、活性和量子 化学研究

合成了[二(2-苯并咪唑亚甲基)胺][咪唑]合Cu(II)Zn(II)Cu(II)高氯酸盐配合物C~5~7H~5~7N~2~1Cu~2Zn(ClO~4)~6.6[(CH~3)~2NCHO],并进行了元素分析、红外和紫外表征,用X射线衍射的方法测定了晶体结构,进行了生物活性测试和量子化学计算。     

Transition Metal Cation Salts in Organic Synthesis

Reaction of lithium diisopropylamide (LDA) with (η⁴-1,3-cyclohexadiene)Fe(CO)₃ complexes bearing functionalized side chains at C-5, under an atmosphere of carbon monoxide, gives bridged bicyclo[3,2,1]octene and bicyclo[3,3,1]nonene systems after electrophilic quenching. Under the same reaction conditions, intramolecular cyclization of acyclic (η⁴- 1,3-butadiene)Fe(CO)₃ complexes with functionalized side chains at the terminal position of the diene ligands furnishes fused bicyclo[3.3,0]octanone and bicyclo[4.3.0]nonanone derivatives after acid quenching. The addition of a variety of the highly functionalized zinc-copper reagents RCu(CN)ZnI to the (η⁷-cycloheptatrienyl)Cr(CO) gives (η⁶-cyclohepta-1,3,5-triene)Cr(CO)₃ complexes with a functionalized side-chain at the C-7 position of the ring. Intramolecular cyclization of ester-subsbtuted adducts using lithium diisopropylamide generates fused bicyclo[5.3.0]decane and bicyclo[5.4.0]undecane derivatives. The addition of a variety of the highly functionalized zinc-copper reagents RCu(CN)Znl to the (η⁴-cyclohexa-1,3-diene)Mo(CO)₂(Cp) at the terminus of the coordinated diene ligand gives [Mo(π-allyl)(CO)₂(Cp)](Cp = cyclopentadienyl) complexes with the functionalized side-chain at the C-4 position of the ring. Intramolecular cyclization of the (π-allyl)molybdenum complex containing a pendant propanoic acid unit generates the δ-lactone derivative.     

Complex Transition Metal Hydrides

Compounds having structural units formed by transition metals and hydrogen have only become known fairly recently. Only the synthesis and structural characterization of ternary metal hydrides A_xM_yH_z in which A is an alkali or alkaline-earth metal and M is a transition metal, led to the discovery of anionic complex groups of the form [MH_z]. Although there are obvious structural similarities to the corresponding halides and oxides, the dynamic properties of the hydride ligand are somewhat unusual and are responsible for numerous phase transformations. Transitions throughout the range from saltlike to metallic behavior make us expect interesting physical properties and applications.     

Synthesis,Crystal Structure and Optical and Photocatalytic Properties of a Discrete Cuprous Iodide Compound with a Transition Metal Complex Cation

With transition metal complex, a discrete cuprous iodide compound, namely, [Ni(phen)_3]_2Cu_6I_(10)(1, phen = 1,10-phenanthroline) has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1(No. 2) with a = 11.2694(2), b = 12.3699(3), c = 15.0387(3) ?, α = 102.840(2), β = 105.215(2), γ = 96.388(2)°, V = 1940.04(7) ?3, Z = 1, Dc = 2.438 g·cm~(-3), F(000) = 1324, R = 0.0256 and w R = 0.0555(I 2σ(I)). Compound 1 features a discrete anionic moiety of [Cu6I10]~(4-) charge-balanced by two metal complexes of [Ni(phen)_3]~(2+). The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant(crystal violet aqueous solution(CV), 50 m L, 1.0 × 10~(-5) M) could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.     

Substitution-Inert Metal Complex Mobile Phases in Non-Suppressed Cation Chromatography

Substitution-inert metal complexes, [Co(edda)(H₂O)₂]⁺, (Co(edda)(en)]⁺, [Co(edda)(dmen)]⁺, [Co(en)₂-(gly)]²⁺, [Co(en)₂(acac)]²⁺, and [Co(trien)(gly)]²⁺ in their nitrate salt solutions are used as eluents in nonsuppressed cation chromatography (where edda = ethylenediamine-N,N′-diacetic acid, en = ethylenediamine, dmen = N,N′-dime-thylethylenediamine, gly = glycine, acac = acetylacetone, and trien = triethylenetetraamine). It is found that all the mono- and di-valent charged complexes can be used to separate alkali and alkaline earth metal cations, respectively. The separations for monovalent cations are sometimes comparable to those using ultrapure HNO₃ solutions. However, the divalent Ca²⁺ and Sr²⁺ ions cannot be resolved using the metal complex eluents. On the other hand, a selected, direct non-suppressed IC separation of zinc(II) and cadmium(II) ions is demonstrated for the first time using a substitution-inert metal complex eluent and a conductivity detector. Comparisons of these eluents with those reported previously, i. e. HNO₃ and ethylenediammonium salt solution are made and explanations are proposed to account for the different selectivities observed where possible. The future development of this technique is also briefly discussed.     

联三吡啶配体组装及其金属络合物性能*

金属-配体间的配位作用是超分子化学中最重要的相互作用之一,寡聚吡啶配体可以与许多过渡金属离子配位,形成具有独特磁、光物理和电化学性质的过渡金属配合物,因此联三吡啶配体过渡金属配合物性能研究引起化学家的广泛关注。本文系统综述了联三吡啶配体及其衍生物的组装策略及其过渡金属配合物的光化学与光物理性能,包括单极、二极及多极配体以及由这类配体组装得到的各种拓扑结构的单核、多核过渡金属配合物,如线型金属寡聚物、金属聚合物、金属大环化合物、有机金属树枝状化合物等,并介绍这些配合物在该领域研究和应用前景。     

Alternate Transition Metal Complex Based Diene Polymerization

Abstract

In the last decade, there has been a tremendous increase in the number of reports on transition metal complex-mediated butadiene homo- and copolymerization. While typical classical titanium, nickel, cobalt, and neodymium based catalysts have been almost exclusively applied to the production of high cis-1,4-polybutadiene, alternative catalyst systems are currently being developed which enable tuning of the polybutadiene microstructure and permit defined changes in polymer properties such as molecular weight distribution and changes in the polymer glass temperature. Besides new products such as high trans-1,4-polybutadiene or a polymer containing a defined amount of 1,2-polybutadiene, there are butadiene copolymers with different amounts of styrene, isoprene, or ethylene. These new materials should lead to new applications especially in the area of tires, high impact polystyrene (HIPS), and ABS. This review elucidates the new developments in the area of transition metal complex-based butadiene homo- and copolymerization focusing mainly on the transition metal catalyst, the polymerization process and the resulting polymers. Mechanistic details are discussed briefly and wherever useful for the understanding of the polymerization reaction.     

Syntheses, Crystal Structures and Theoretical Calculation of Two Transition Metal Dinuclear Complexes

Two transition metal dinuclear complexes of [Mn2（OOCC6H4SSC6H4COO）- （Phen）2（H20）]n 1 and [CuE（OOCC6H4S）2（Phen）2] 2 were hydrothermally synthesized by the reaction of equivalent metal dichloride with 2,2＇-dithiobis（benzoic acid） （HE-DTBB）. Structure analysis indicates that each Mn2＋ ion in I is coordinated by one chelate phen ligand, one bridging water molecule and three DTBB ligands forming Mn2＋ dinuclear units which are further linked into one-dimensional chain by DTBB ligand. Under similar reaction conditions, the 2,2＇-dithio- his（benzoic acid） ligand undergoes thiol reduction to form 2-mercaptobenzoic （H-2-MBA） in 2 where two Cu2＋ ions are coordinated by phen and MBA ligands only constructing a dinuclear unit.     

Syntheses and Molecular Structure of Dinuclear Transition Metal Complexes Bridged by Dipyridylamine Derivative Ligands

Stable dinuclear transition metal complexes,[(η⁶‐C₆H₆)₂Ru₂(L1)Cl₂]²⁺ ( 1 ), [(η⁶‐p‐iPrC₆H₄Me)₂Ru₂(L1)Cl₂]²⁺ ( 2 ), [(η⁶‐C₆Me₆)₂Ru₂(L1)Cl₂]²⁺ ( 3 ), [(η⁶‐C₆H₆)₂Ru₂(L2)Cl₂]²⁺ ( 4 ),[(η⁶‐p‐iPrC₆H₄Me)₂Ru₂(L2)Cl₂]²⁺ ( 5 ), [(η⁶‐C₆Me₆)₂Ru₂(L2)Cl₂]²⁺ ( 6 ), [(η⁵‐C₅Me₅)₂Rh₂(L1)Cl₂]²⁺ ( 7 ), [(η⁵‐C₅Me₅)₂Ir₂(L1)Cl₂]²⁺ ( 8 ),[(η⁵‐C₅Me₅)₂Rh₂(L2)Cl₂]²⁺ ( 9 ), and [(η⁵‐C₅Me₅)₂Rh₂(L2)Cl₂]²⁺ ( 10 ), with the bis‐bidentate ligands 1,3‐bis(di‐2‐pyridylaminomethyl)benzene (L1) and 1,4‐bis(di‐2‐pyridylaminomethyl)benzene (L2), which contain two chelating dipyridylamine units connected by an aromatic spacer, were synthesized. The cationic dinuclear complexes were isolated as their hexafluorophosphate salts and characterized by using a combination of NMR, IR, and UV/Vis spectroscopic methods and mass spectrometry. The solid‐state structure of complex 8 as a representative was determined by X‐ray structure analysis.