On-demand generation of an efficient catalyst for pyridine formation from unactivated nitriles and alpha,omega-diynes using CoCl2-6H2O, dppe, and Zn

[reaction: see text] A highly practical, general method for catalytic formation of substituted pyridines from a variety of unactivated nitriles and alpha,omega-diynes is given. The reactions which were catalyzed by 5 mol % of dppe/CoCl2-6H2O in the presence of Zn powder (10 mol %) could proceed at rt to approximately 50 degrees C with high functional compatibility and regioselectivity.     

Synthesis, characterization and nonlinear absorption of novel octakis-POSS substituted metallophthalocyanines and strong optical limiting property of CuPc

In this study, the preparation of some novel metallophthalocyanine (MPcs) complexes substituted with octakis(mercaptopropylisobutyl-POSS) functional group was achieved. By the reaction of [1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane 1 with 4,5-dichloro-1,2-dicyanobenzene 2 in THF as the solvent in the presence of K2CO3 as the base, the phthalonitrile derivative 3 was synthesized. Compound 3 reacted with CoCl2 x 6H2O in ethylene glycol to furnish a novel cobalt(II) phthalocyanine . The tetramerization of 3 with urea and CuCl in the absence of solvent gave the novel Cu(II) phthalocyanine 4; while with Zn(OAc)2 x 2H2O in dry DMF gave the novel zinc(ii) phthalocyanine 6. The structures of the target compounds were confirmed by elemental analysis, UV/VIS, IR, MALDI-TOF MS and 1H NMR spectra. Nonlinear absorptions of MPcs in chloroform solution were investigated by using Z-scan measurement technique with 4 ns pulses at 532 nm wavelength. While CuPc 5 showed very high nonlinear absorption, MPcs 4 and 6 did not show considerable nonlinear absorption. Investigations of optical limiting properties of 5 revealed that this material is a very good candidate for optical limiting applications.     

New compounds from tellurocyanide rhenium cluster anions and 3d-transition metal cations coordinated with ethylenediamine

The compounds [Ni(en)(3)](2)[Re(6)Te(8)(CN)(6)].10H(2)O (1), [Ni(NH(3))(4)(en)](2)[Re(6)Te(8)(CN)(6)].2H(2)O (2), [Ni(NH(3))(2)(en)(2)][(Ni(en)(2))(3)(Re(4)Te(4)(CN)(12))(2)].38H(2)O (3), [Co(NH(3))(2)(en)(2)](2)[(Co(en)(2))Re(6)Te(8)(CN)(6)]Cl(2).H(2)O (4),and [(Zn(H(2)O)(en)(2))(Zn(en)(2))Re(6)Te(8)(CN)(6)].3H(2)O (5) (en = ethylenediamine) have been synthesized and characterized. Compounds 1, 4, and 5 have been synthesized by the diffusion of an aqueous (for 1 and 5) or an ammonia (for 4) solution of Cs(4)[Re(6)Te(8)(CN)(6)].2H(2)O into a glycerol solution of NiCl(2).6H(2)O (for 1), CoCl(2).6H(2)O (for 4), or ZnCl(2) (for 5). Compounds 2 and 3 have been synthesized by the reaction of an aqueous solution of Cs(4)[Re(6)Te(8)(CN)(6)].2H(2)O (for 2) or K(4)[Re(4)Te(4)(CN)(12)].5H(2)O (for 3) with an ammonia solution of Ni(en)(2)Cl(2). Compounds 1 and 2 are ionic whereas compounds 4 and 5 are one-dimensional polymers. Compound 3, a two-dimensional polymer, possesses hexagonal shaped channels of approximate diameter 10-12 A. Because the framework of compound 3 is robust, it is an attractive host for guest molecules of appropriate size and shape. The potential "guest" volume is about 37% of the unit cell volume.     

Synthesis and characterization of mono- and micro6-sulfato hexanuclear zinc complexes of a new symmetric dinucleating ligand

Zinc complexes of a new symmetric dinucleating ligand, N,N'-Bis[2-carboxybenzomethyl]-N,N'-Bis[carboxymethyl]-1,3-diaminopropan-2-ol (H5ccdp) with mixed donating groups, have been studied in the solid state as well as in solution. In methanol, the reaction of stoichiometric and substoichiometric amounts of Zn(ClO4)2 x 6H2O and the ligand H5ccdp, in the presence of K2CO3 or Et3N, afforded a mononuclear zinc complex, [Zn(H2O)6][Zn(H2ccdp)(H2O)2]2 x 12H2O (1). The solid state structure of 1 contains two units of the zinc-ligand anion, [Zn(H2ccdp)(H2O)2]-, and one [Zn(H2O)6]2+ counter cation. The Zn(II) center of the anion is in a distorted octahedral geometry. However, in methanol, the reaction of ZnSO4 x 7H2O and the ligand Hsccdp in the presence of NaOH afforded a unique micro6-sulfato hexanuclear zinc complex, Na6[Zn6(ccdp)3(micro6-SO4)](OH) x 10.5H2O (2). The structure of 2 contains a [ZnII6(micro6-SO4)] core unit which is held together by three heptadentate bridging ligands, ccdp5-. Three of the Zn(II) centers are in highly distorted square pyramidal geometry, the other three Zn(II) centers are in a distorted octahedral geometry.     

Boxes, helicates, and coordination polymers: a structural and magnetochemical investigation of the diverse coordination chemistry of simple pyridine-alcohol ligands

A structurally diverse array of polynuclear complexes has been identified and structurally characterized from the reaction of 6-methylpyridine-2-methanol (1) with a range of cobalt(II) salts under a variety of reaction conditions. A tetranuclear cubane, [Co4(1-H)4Cl4(H2O)3(CH3OH)], was isolated from the reaction of 1 with CoCl2.6H2O and NaOH in MeOH, and a tetranuclear double cubane, [Co4(1-H)6(NO3)2], was isolated from the reaction of 1 with Co(NO3)2.6H2O and NEt3 in MeOH. A bowl-shaped trinuclear complex, [Co3(1-H)3Cl3(dmso)], which features a triply bridging dmso ligand, assembled upon mixing 1 and CoCl2.6H2O in dmso. A 1-D coordination polymer, [Co(1)2(SO4)](infinity), where the sulfate ligands bridge "[Co(1)2]" units in a mu2:eta1 fashion to build up the polymer structure, was isolated from the reaction of 1 with CoSO4.7H2O. The reaction of the structurally related ligand 8-hydroxyquinaldine (2) with a mixture of CoCl2.6H2O and Co(OAc)2.4H2O lead to the formation of the tetranuclear double cubane, [Co4(2-H)6Cl2]. Temperature-dependent magnetic measurements have also been performed for these five complexes along with the hydrogen-bonded helicate [Co2(1)2(1-H)2]. The hydrogen bonds of the helicate mediate antiferromagnetic interactions between the cobalt(II) centers (J = -3.18(9) cm(-1), g = 2.25(2)). The sulfate bridging ligands of [Co(1)2(SO4)](infinity) are poor mediators of magnetic exchange. The Co(II) centers in the double-cubane complexes [Co4(1-H)6(NO3)2] and [Co4(2-H)6Cl2] are strongly antiferromagnetically coupled to each other at low temperature to give an S = 0 ground state. [Co4(1-H)4Cl4(H2O)3(MeOH)] exhibits rather complicated magnetic behavior; however, we did not observe any evidence for single-molecule magnetism as was seen for structurally related complexes.     

Zn(NO_3)_2·6H_2O/2,4,6-trichloro-1,3,5-triazine(TCT) a mild and selective system for nitration of phenols

<正>Certain phenols and naphthols were nitrated regioselectively with Zn(NO_3)_2·6H_2O/TCT in acetonitrile as solvent at room temperature and short reaction time in good yields.The reaction condition was mild.TCT is a cheap and commercially available reagent.It performed as an acid catalyst in this transformation.     

一维链状钴(Ⅱ)和锌(Ⅱ)配合物的合成及结构表征

本文以乙酰丙酮和1,4-二(邻氨基苯氧基)丁烷进行缩合得到Schiff碱配体L,再分别同CoCl2.6H2O和ZnCl2.4H2O进行配位反应,得到了2个配合物[CoLCl2]n(1)和[ZnLCl2]n(2),并用元素分析,FTIR和X-射线单晶衍射进行了表征。结果表明,配合物1和2属于异质同晶,均属于正交晶系,空间群均是Pna21。在化合物1和2中,每个Co(Ⅱ)和Zn(Ⅱ)的配位环境均为扭曲四面体,2个配合物中每个配体L通过其两臂乙酰丙酮亚胺单元的端基氧原子同2个金属离子配位桥联形成一维链结构。     

Synthesis of novel chiral and acentric coordination polymers by the reaction of zinc or cadmium salts with racemic 3-pyridyl-3-aminopropionic acid

Under hydrothermal (solvothermal) reaction conditions chiral compounds 1, 2, and 3 and one acentric compound 4 were obtained by the reaction of Zn(2+) or Cd(2+) with racemic 3-(3-pyridyl)-3-aminopropionic acid (rac-HPAPA). Compounds 1 and 2 crystallized in chiral space group P2(1)2(1)2(1). At 105 degrees C, racemic 3-pyridyl-3-aminopropionic acid (rac-HPAPA) reacted with Zn(ClO4)(2).6 H2O and dehydrogenated in situ to form the first chiral coordination polymer [Zn[(E)-3-C(5)H4N-C(NH2)=CH-COO]]ClO4 (1) with a beta-dehydroamino acid. Beyond 120 degrees C, the reaction of rac-HPAPA with Zn(ClO4)(2).6 H2O deaminates in situ to form chiral coordination polymer [Zn[(E)-3-C5H4N-CH=CH-COO](OH)] (2). At relatively low temperatures (70 degrees C), the solvothermal reaction of Zn(NO3)(2).6 H2O with rac-HPAPA in methanol does not lead to any change in the ligand and results in the formation of a chiral (P2(1)2(1)2(1)) coordination polymer [Zn(papa)(NO3)] (3). The same reaction of Cd(ClO4)(2).6 H2O with HPAPA also does not lead to any change in ligand and results in the formation of noncentric (Cc) coordination polymer [Cd(papa)(Hpapa)]ClO4.H2O (4). The network topology of both 1 and 3 is 10,3a, while 2 has a diamondoid-like (KDP-like, KDP=potassium dideuterophosphate) network. Particularly interesting from a topological perspective is that 4 has an unprecedented three-dimensional network. Compounds 1, 2, 3, and 4 are all second harmonic generation (SHG) active with 1 exhibiting the strongest response, while only 4 also displays good ferroelectric properties.     

从配位聚合物到单分子化合物的转化：Demko-Sharpless四唑合成法制备两个新颖的Co(II)配合物

The reaction of CoCl₂·6H₂O with 4-cyanopyridine N-oxide in the present of NaN₃ affords two novel complexes, {[(POTZ)(H₂O)₂N₃]Co(H₂O)} (1) and Co(POTZ)₂(H₂O)₄ (2) (POTZ=4-tetrazolyl pyridine N-oxide), which are two different phases yielded at different stages of a single Demko-Sharpless′ tetrazole synthesis reaction. Surprisingly the 1D chain coordination polymer 1 is almost completely converted into monomeric complex 2 in this reaction, and, in a separate test, 2 also can be converted into 1. CCDC: 641222, 1; 641223, 2.     

A new route for preparing coordination polymers from hydrothermal reactions involving in situ ligand synthesis

The coordination chemistry of inorganic cobalt salt and the organic ligands H(4)bbh (=benzene-1,2,4,5-bihydrazide) and H(3)bcbh (=benzene-4-carboxylate-1,2-bihydrazide) generated through the in situ hydrothermal acylate reaction of H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid) and H(3)btc (=benzene-1,2,4-tricarboxylic acid) with hydrazine hydrate, respectively, has been investigated. Three new coordination polymers were prepared and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The compound [Co(micro(3)-H(2)bbh)(phen)](n)() (1) (triclinic space group P with a = 9.762(4) A, b = 10.169(4) A, c = 11.143(4) A, alpha = 80.96(3) degrees, beta = 64.49(3) degrees, gamma = 71.88(3) degrees, Z = 2) was synthesized from the reaction of CoCl(2).6H(2)O, H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid), N(2)H(4).H(2)O, phen (=1,10-phenanthroline) and H(2)O, and consists of one-dimensional double-chains. [Co(micro(4)-H(2)bbh)(H(2)O)(2)](n)() (2) (monoclinic space group P2(1)/c with a = 6.8687(5) A, b = 7.5943(6) A, c = 10.0401(6) A, beta = 95.250(4) degrees, Z = 2) was generated by the combination of CoCl(2).6H(2)O, H(4)bta, N(2)H(4).H(2)O, and H(2)O. It adopts a three-dimensional structural motif in the solid state with channels consisting of 20-numbered rings. [Co(micro(3)-Hbcbh)(bpy)](n)() (3) (monoclinic space group Cc with a = 9.9464(13) A, b = 23.685(5) A, c = 7.9491 (16) A, beta = 117.677(13) degrees, Z = 4) was obtained from the mixture of CoCl(2).6H(2)O, N(2)H(4).H(2)O, H(3)btc (=benzene-1,2,4-tricarboxylic acid), bpy (=2,2'-dipyridyl), and H(2)O, and features a two-dimensional plane. The results of magnetic research indicate that there exist antiferromagnetic interactions between Co centers in both compounds 1 and 2.     

过渡金属配合物连接的多金属钒酸盐[Co(o-phen)]V2O6·H2O的水热合成和晶体结构

多金属氧酸盐 ( POMs)由于结构新奇 ,物理性能优异 ,在催化、医药、材料和光化学等领域有应用前景 ,而受到人们广泛关注 [1～ 8] .近年来 ,水热技术和有机指导剂的引入促进了 POMs的有机 -无机杂化材料如 [N( CH3) 4]5V18O4 6 [2 ]和 [V4 O10 ( phen) 2 ][3]等研究的迅速发展 .以上化合物多数仅以有机胺为抗衡离子或直接配位连接到无机骨架上 .而以过渡金属配合物为结构导向剂的合成策略 ,最近才引起人们的重视[9～ 11] .本文以钒酸盐 -过渡金属配合物作为研究体系 ,在水热条件下合成了一种未见文献报道的由新型过渡金属配合物连接的…     

Crystal engineering of a versatile building block toward the design of novel inorganic-organic coordination architectures

Six novel inorganic-organic coordination supramolecular networks based on a versatile linking unit 4-pyridylthioacetate (pyta) and inorganic Co(II), Cu(II), Ag(I), Zn(II), Mn(II) and Pb(II) salts have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of CoCl(2).6H(2)O with Hpyta afforded a neutral mononuclear complex [Co(pyta)(2)(H(2)O)(4)](1), which exhibits a two-dimensional (2-D) layered architecture through intermolecular O-HO interactions. Reaction of CuCl(2.2H(2)O with Hpyta yielded a neutral one-dimensional (1-D) coordination polymer [[Cu(pyta)(2)(H(2)O].0.5H(2)O](n)(2) consisting of rectangle molecular square units, which show a three-dimensional (3-D) supramolecular network through S...S and O-H...O weak interactions. However, when AgNO(3), Zn(OAc)(2).2H(2)O or MnCl(2).4H(2)O salts were used in the above self-assembled processes, the neutral 2-D coordination polymers [Ag(pyta)](n)(3), [[Zn(pyta)(2)].4H(2)O](n)(4) or [[Mn(pyta)(2)(H(2)O)]](n)(5) with different topologies were obtained, respectively. While substituting the transition metal ions used in 1-5 with Pb(OAc)(2).3H(2)O, a one-dimensional coordination polymer [Pb(pyta)(2)](n)(6), which shows a novel 2-fold interpenetrating 2-D supramolecular architecture through weak SS interactions, was isolated. It is interesting to note that the building block pyta anion exhibits different configurations and coordination modes in the solid structures of complexes 1-6. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal centers, play a critical role in construction of these novel coordination polymers or supramolecules. The spectral and thermal properties of these new materials have also been investigated.     

Zinc(II) ortho-hydroxyphenylhydrazo-β-diketonate complexes and their catalytic ability towards diastereoselective nitroaldol (Henry) reaction

The zinc(II) complexes with ortho-hydroxy substituted arylhydrazo-β-diketonates [Zn(2)(CH(3)OH)(2)(μ-L(1))(2)] (5), [Zn{(CH(3))(2)SO}(H(2)O)(L(2))] (6), [Zn(2)(H(2)O)(2)(μ-L(3))(2)] (7) and [Zn(H(2)O)(2)(L(4))]·H(2)O (8) were synthesized by reaction of a zinc(II) salt with the appropriate hydrazo-β-diketone, HO-2-C(6)H(4)-NHN=C{C(=O)CH(3)}(2) (H(2)L(1), 1), HO-2-O(2)N-4-C(6)H(3)-NHN=C{C(=O)CH(3)}(2) (H(2)L(2), 2), HO-2-C(6)H(4)-NHN=CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(3), 3) or HO-2-O(2)N-4-C(6)H(3)-NHN=[CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(4), 4). They were fully characterized, namely by X-ray diffraction analysis that disclosed the formation of extensive H-bonds leading to 1D chains (5 and 6), 2D layers (7) or 3D networks (8). The thermodynamic parameters of the Zn(II) reaction with H(2)L(2) in solution, as well as of the thermal decomposition of 1-8 were determined. Complexes 5-8 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The threo/erythro diastereoselectivity of the β-nitroalkanol products ranges from 8:1 to 1:10 with typical yields of 80-99%, depending on the catalyst and substrate used.     

Synthesis and magnetism of oxygen-bridged tetranuclear defect dicubane Co(II) and Ni(II) clusters

Reaction of aqueous/ethanolic solutions of CoCl2.6H2O and nitrilotripropionic acid (H3ntp=N(CH2CH2COOH)3) in the presence of potassium hydroxide affords the hydroxy-bridged tetranuclear cluster [Co4mu3-OH)2(H2O)6(ntp)2].2H2O (1). The Ni(II) analogue [Ni4(mu3-OH)2(H2O)6(ntp)2].2H2O (2) can also be isolated using aqueous solutions and Ni(SO4).7H2O as metal salt. With small changes in reaction conditions the methoxy-bridged analogue, [Ni4(mu3-OMe)2(H2O)6(ntp)2](3), can also be isolated. In these tetramers the M(II) ions are oxygen-bridged and exhibit a defect dicubane-like core with two missing vertices. The magnetic properties have been studied for all three clusters and reveal competing antiferromagnetic and ferromagnetic interactions between the four Co(II) ions in 1 and ferromagnetic coupling between the four Ni(II) ions in 2 and 3. In all three compounds the individual clusters order antiferromagnetically at Neel temperatures below 1 K.     

Construction of metal-organic frameworks: versatile behaviour of a ligand containing mono- and bidentate coordination sites

Five new coordination polymers based on a new 2,2'-bipyridine derived ligand N,N'-bis(pyridin-4-yl)-2,2'-bipyridine-5,5'-dicarboxamide (=L) are reported herein. Isostructural three-dimensional coordination polymers with a rare (4,6)-connected network of {4(4).6(2)}(3){4(6).8(9)}(2) topology were synthesised from Cu(NO(3))(2), Zn(NO(3))(2) or a mixture of Cu(NO(3))(2)/Fe(BF(4))(2) with L in complexes {[Cu(5)L(6)]·(NO(3))(10)·(H(2)O)(18)}(∞) (1), {[Zn(5)L(6)]·(NO(3))(10)·(H(2)O)(18)}(∞) (2) and {[Fe(x)Cu(y)L(6)]·(NO(3))(10)·(H(2)O)(18)}(∞) (3; where x+y=5). Complexes with two-dimensional grid structures resulted from treatment with CoCl(2) or Cd(NO(3))(2) with L in complexes {[CoLCl(2)]·DMF}(∞) (4) and {CdL(NO(3))(2)}(∞) (5).     

含有3,4-吡唑二甲酸的锌(Ⅱ)配合物:合成、结构和荧光性质（英文）

3,4-吡唑二甲酸(H3pdc)与Zn(NO3)2·6H2O在不同的条件下反应制得了2个新的配合物:[Zn(H2pdc)2(H2O)2]·2H2O(1)和[Zn2(Hpdc)2(H2O)6]·2H2O(2)。X射线衍射分析表明,1和2分别是单核和双核结构。H3pdc部分脱质子后的阴离子配体在1和2中采用的是N,O-螯合(H2pdc-)以及μ2-κN,O∶κN桥联(Hpdc2-)配位模式。在这2个配合物中,相邻的零维组分通过分子间氢键(O-H…O,N-H…O和C-H…O)作用形成三维超分子结构。此外我们还研究了配合物1和2的热稳定性和荧光性能。     

Synthesis and Crystal Structure of Co(C_6NO_2H_4)_3. H_2O

1INTRoDUCTIONAlotofresultsoncobaltcomplexstructureshavebeenreportedforseveraldecades.Theinterestofresearchinthisfieldhasneverbeenreducedbecausethecobaltcomplexesplayaveryimportantroleinthelifescienceandcatalysis,etc[1-6).WereportherethesynthesisandstructureofcomplexCo(C,NO,H'),.H,O.2EXPERIMENTALAllreagentsandsolventsusedareofARgradefromcommericalsourceswithoutfurtherpurification.ThetitlecompoundCo(C,NO,H,),.H,Owassynthesizedbythefollowingmethod.When2.4g(ca.1mmol)ofCoCl2.6H2Ow…     

Cyclotriphosphazene hydrazides as efficient multisite coordination ligands. eta(3)-fac-non-geminal-N(3) coordination of spiro-N(3)P(3)[O(2)C(12)H(8)][N(Me)NH(2)](4) (L) in L(2)CoCl(3) and L(2)M(NO(3))(2) (M = Ni, Zn, Cd)

The cyclophosphazene tetrahydrazide spiro-N(3)P(3)[O(2)C(12)H(8)][N(Me)NH(2)](4) (L) functions as a multisite coordination ligand and affords L(2)CoCl(3).2CH(3)OH (4), L(2)Ni(NO(3))(2).2CHCl(3).2.5H(2)O (5), L(2)Zn(NO(3))(2).2CH(3)CN.2H(2)O (6), and L(2)Cd(NO(3))(2) (7). Each of the cyclophosphazene ligands that is involved in coordination to the metal functions as a non-geminal-N(3) donor coordinating through one ring nitrogen atom and two non-geminal-NH(2) nitrogen atoms. The coordination geometry around the metal ion in 4-6 is approximately octahedral while it is severely distorted in the case of 7.     

Crystal Structure of Borophosphate with 6_1 Screw Axis Helices

1 INTRODUCTION Most materials with nonlinear optical pro- perties and electro-optical applications are either borates or phosphates. LBO(LiB3O5), KTP(KtiO- PO4), BBO(b-BaB2O4) and KDP(KH2PO4) are well- known commercially and extensively used for different optical elements. In recent years, the compounds combined both borate and phosphate groups have been synthesized and structurally characterized with quite different anionic partial structures. In particular, the use of hydrot…     

Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O: a zinc phosphonate cluster with a drum-like cage structure

Direct reaction of hydroxy(2-pyridyl)methylphosphonic acid with zinc sulfate under hydrothermal conditions results in the formation of the novel heptanuclear cluster compound [Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O (1). The inorganic core of the cluster can be described as a cylindrical drum made up of six Zn atoms bridged by six {CPO3} units that is centered by a seventh Zn atom. Crystal data: monoclinic, C2/c, a = 22.690(2) A, b = 16.675(2) A, c = 18.151(2) A, beta = 93.390(2) degrees.