Bis(Saccharinato)Nickel(II) Complexes with 2-Aminomethyl and -Ethylpyridines. Syntheses,Crystal Structures,Spectral and Thermal Analyses of trans-[Ni(sac-N)2(ampy-N,N′)2] and trans-[Ni(sac-O)2(aepy-N,N′)2]

The trans-bis(saccharinato)nickel(II) complexes with 2-aminomethylpyridine (ampy) and 2-aminoethylpyridine (aepy) have been prepared and characterized by elemental analyses, i.r., u.v.–vis., magnetic measurements and single crystal X-ray diffraction. Both structures consist of discrete molecules of the title complexes, in which the nickel(II) ion lies on an inversion centre and is octahedrally coordinated by two bidentate (N,N) ampy or aepy ligands and two anionic sac ligands, occupying trans positions. The most interesting feature of the complexes is the coordination of sac. In [Ni(sac)₂(ampy)₂], sac is N-bonded, whereas it is O-coordinated in [Ni(sac)₂(aepy)₂]. The i.r. spectra and thermal behaviour of both complexes are discussed in detail.     

Reaction of Adenine and Guanine with [Ru(RaaiR′)2(EtOH)2](ClO4)2 · Spectral and Electrochemical Characterization of the Products [RaaiR′ = 1-Alkyl-2-(arylazo)-Imidazole]

[Ru(RaaiR)₂(EtOH)₂](ClO₄)₂[RaaiR= 1-alkyl-2-(arylazo)imidazole, p-R-C₆H₄-N = N-C₃H₂N-N(1)-R, R = H (a), Me (b), Cl (c), R= Me (1, 3), Et (2, 4)] reacts with nucleobases [NB – adenine (A), guanine (G)] in aqueous EtOH to give red–violet mixed ligand complexes of the type [Ru(RaaiR)₂(NB)(H₂O)](ClO₄)₂. The solution electronic spectra exhibit a strong MLCT band at 540–560 nm in MeCN. The cyclic voltammogram shows a Ru^III/Ru^II couple at 1.3–1.4 V versus Ag/AgCl along with three successive ligand reductions.     

Syntheses and(Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)2Cl]·ClO4 and [Zn(bipy)2Cl]·BF4

Two new transition metal complexes, [Ni(bipy)2Cl]·ClO4 (bipy = 2,2'-bipyridine) 1 and [Zn(bipy)2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776(1), b = 12.067(1), c = 16.146(2)(A), β= 93.021(2)o, V = 2031.9(4)(A)3, Mr = 505.98, Dc = 1.654 g/cm3, μ = 1.255 mm-1, F(000) = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with Ⅰ ＞ 2σ(I). For 2, a = 10.758(4), b = 12.058(4), c = 16.135(5) (A), β = 104.57(1)o, V = 2025.7(12) (A)3, Mr = 500.00, Dc = 1.639 g/cm3, μ = 1.396 mm-1, F(000) = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with Ⅰ ＞ 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen- sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy …anion…bipy--M hydrogen bonding interactions between the chelating ligands of bipy and anion.     

Dimer of Bis[trans-5-methyl-2-[2-(4-methoxylphenyl) ethenyl]-benzoxazole]di-μ-nitratosilver(I)

The title complex [AgNO3(C17H15NO2)2]2 was synthesized and characterized by X-ray diffraction analysis. The compound crystallizes in triclinic, space group Pī with a = 11.226(7), b = 11.906(7), c = 12.144(7) (A。), α = 99.796(10), β = 91.631(10), γ = 101.225(10)°, V = 1565.6(16)(A。)3, Z = 1, Mr = 1400.96, Dc = 1.486 g/cm3, F(000) = 716 and μ(Mo-Kα) = 0.697 mm-1. The final R and wR are 0.0401 and 0.0995, respectively for 5492 independent observable reflections with I > 2σ(I). The results show that the central Ag atom is four-coordinated with two O atoms from two distinct NO3- anions and two N atoms from two trans-5-methyl-2-[2-(4-methoxylphenyl)ethenyl]- benzoxazole ligands, and the two Ag atoms bridged with two O atoms give an interesting Ag-O-Ag-O parallelogram structure. The coordination sphere of Ag atom exhibits a heavily distorted tetrahedral geometry and the coordination angles lie in the range of 66.73(12)～129.59(10)°. The intra- molecular dihedral angles between the benzoxazolyl and phenyl planes are 4.1(3) and 2.9(3)°, respectively.     

Synthesis and Crystal Structure of a [Cu(HTren)Cl2]ClO4·H2O Complex (Tren = Tris(2-aminoethyl)amine)

The title complex [Cu(HTren)Cl2]ClO4·H2O (Tren = tris(2-aminoethyl)amine) was crystal (CuC6H21Cl3N4O5) is of triclinic, space group P-1, with a = 8.2689(2), b = 8.4503(3), c=11.6801(4)(A), a = 96.9350(10), β= 108.2440(10), γ = 90.7550(10)°, V= 768.32(4)(A)3, Z= 2, Mr=399.16, Dc= 1.725 g/cm3,μ= 1.962 mm-1, F(000) = 410, T= 293(2) K, the final R = 0.0479 and wR = 0.1339 for 2659 observed reflections with I ＞ 2σ(I). X-ray single-crystal structure analysis reveals that the copper(Ⅱ) atom adopts a slightly distorted square-pyramidal geometry. The distances between Cu and N atoms (N(1), N(2), N(3)) range from 1.975(4) to 2.116(3)(A). The bond lengths of Cu-Cl(1) and Cu-Cl(2) are 2.309(10) and 2.591(10) (A), respectively. The whole crystal presents a three-dimensional network structure by hydrogen bonds.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

The crystal and molecular structures of aqua(1,4,7,10,13-pentaazacyclopentadecane)nickel(II) nitrate perchlorate [Ni[15]aneN5·H H2O](NO3)(ClO4) and (1,5,9,13,17-pentaazacycloeicosane)-nikel(II) nitrate hydrate [Ni[20]aneN5](NO3)2·H2O

Summary The structures of Ni^II complexes of the macrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, [15]aneN₅ and 1,5,9,13,17-pentaazacycloeicosane, [20]aneN₅ have been determined. [Ni(C₁₀H₂₅N₅)H₂O]-(NO₃)(ClO₄) monoclinic, space group P2₁/n,a=8.265(3)Å,b=6.201(6)Å,c=13.672(4)Å, =93.35(3)°· 2394 unique reflections were used in the structure determination and the refinement proceeded to an R value of 0.045. The ligand is coordinated to the metalvia all five nitrogens in theracemic conformation and a water molecule completes the coordination sphere of the metal ion. The complex cation shows considerable distortion from octahedral geometry which may rationalise the unusual spectroscopic properties and the low enthalpy of formation of the complex cation. [Ni(C₁₅H₃₅N₅)](NO₃)₂·H₂O monoclinic, space group P2₁/n,a=15.437(9)Å,b=9.573(6)Å,c=15.942(8)Å, =109.24(4)°. 2715 unique observed reflections were used in the structure refinement which proceeded to an R value of 0.035. The five nitrogens of the macrocycle are bound to Ni(II) in a distorted square pyramidal coordination geometry. The Ni^II lies 0.35Å above the basal plane of the four nitrogen atoms.     

[Mn(H2O)4(NCS)2](18-冠-6)的分子和晶体结构

报导了[Mn(H2O)4(NCS)2](18-冠-6)单晶的X射线结构分析.它的晶体正交晶系.锰(II)与两个硫氰酸根,四个水分子配合形成顺式八面体的配位分子,并通过其中的水分子与18-冠-6以氢键结合.     

Cobalt(II) and nickel(II) complexes of N(4′) substituted 3- and 4-acetylpyridine thiosemicarbazones

Co^II and Ni^II complexes of N(4)-methyl and N(4)-ethyl thiosemicarbazones derived from 3- and 4-acetylpyridine have been prepared and characterized by microanalyses, magnetic susceptibility and molar conductivity measurements and by their electronic, i.r. and n.m.r. (in the case of Ni^II complexes) spectra.     

Synthesis and characterisation of [Ag2Pt4(μ-S)4(PPh3)8](BF4)2 · 0.25CHCl3

[Pt₂(μ₂-S)₂(PPh₃)₄] functions effectively as a bridging bidentate ligand towards Ag⁺ to form [Ag₂Pt₄(μ₃-S)₄(PPh₃)₈]²⁺. A single crystal X-ray crystallographic anaylsis of the BF₄⁻ salt has demonstrated that both Ag⁺ ions are linearly coordinated to the sulphur atoms, but the small bite angle of the [Pt₂(μ-S)₂(PPh₃)₄] ligand leads to an Ag…Ag contact distance of only 2.815(4) Å.     

Syntheses and characterization of new MnII and FeII complexes with 4′-(4-pyridyl)-2,2′ : 6′,2″-terpyridine (pyterpy), [Mn(pyterpy)(MeOH)2(OAc)](ClO4) and [Fe(pyterpy)2](SCN)2 · MeOH

Two new Mn^II and Fe^II complexes with 4′-(4-pyridyl)-2,2′ : 6′,2″-terpyridine (pyterpy), [Mn(pyterpy)(MeOH)₂(OAc)](ClO₄) (1) and [Fe(pyterpy)₂](SCN)₂ · MeOH (2) have been synthesized and characterized by CHN elemental analysis, IR spectroscopy, and structurally analyzed by single-crystal X-ray diffraction. The thermal stabilities of these compounds were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The potentially tetradentate pyterpy ligand is a tridentate donor to both Mn(II) and Fe(II). The non-coordinated pyridyl interacts via O–H ··· N and C–H ··· N hydrogen bonds with adjacent molecules in 1 and 2, respectively, to form inversion symmetric dimers. Compound 1 is further extended into infinite hydrogen bonded chains via pairs of O–H ··· O_acetate hydrogen bonds.     

New trans-[Re6S8(CN)4L2] n− Rhenium Cluster Complexes: Syntheses, Crystal Structures and Properties

Reaction of polymeric compound Cs₄[Re₆S₈(CN)₄S_2/2] with aqueous solution of KOH led to formation of trans-[Re₆S₈(CN)₄(OH)₂]⁴⁻ anion which was crystallized in ordered Cs_1.68K_2.32[Re₆S₈(CN)₄(OH)₂] · 2H₂O (1a) and disordered Cs_1.83K_2.17[Re₆S₈(CN)₄(OH)₂] · 2H₂O (1b) modifications. The presence of two types of apical ligands, inert cyanides and labile hydroxides, opened a way to other trans-[Re₆S₈(CN)₄L₂] ⁿ⁻ rhenium cluster complexes: trans-[Re₆S₈(CN)₄Cl₂]⁴⁻, trans-[Re₆S₈(CN)₄(H₂O)Br]³⁻, and trans-[Re₆S₈(CN)₄Br₂]⁴⁻, crystallized as Cs_1.84K_1.16(H)[Re₆S₈(CN)₄Cl₂] (2), Cs_1.68K_1.32[Re₆S₈(CN)₄(H₂O)Br] (3), (Me₄N)₃(H₅O₂)[Re₆S₈(CN)₄Br₂] (4), and CsK{Cu(H₂O)₂[Re₆S₈(CN)₄Cl₂]} · 4H₂O (5) salts.     

[Cu(dppp)2](ClO4)的合成、结构和性质

近年来各种磷桥过渡金属双核配合物由于其特殊的结构、新奇的反应性能及催化行为,受到人们的普遍关注,对它们的研究已成为有机金属化学的一个前沿领域.其中双齿膦配体以dppm,dppe最为常见[1],而有关dppp的铜配合物文献报导甚少.Cu(Ⅰ)配合物的合成相对其它过渡金属配合物的合成难度要大,且以往含双膦配体铜配合物的合成大多数是由一价铜盐开始,这样合成的配合物往往不太稳定.本文利用dppp配体的还原性,从二价铜盐开始,探索出一种较为有效的合成铜配合物的方法,并合成了一个含dPPP铜配合物:[Cu(dPPP)2](C1O4),通过元素分析、IR、磁化率、循环伏安、摩尔电导、TG等对其进行了表征,并研究了磁性,测定了[Cu(dppp)2](C1O4)的晶体结构.     

Syntheses and crystal structures of oxovanadium(V) complexes derived from N′-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide and 2-hydroxy-N′-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide

Reactions of bis(acetylacetonato)oxovanadium(IV) with N??-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide (H₂HNB) and 2-hydroxy-N??-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide (H₂HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]₂ (I) and [VO(OMe)(HHB)] (II). The complexes I and II have been characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/n, a = 8.208(2), b = 14.528(3), c = 16.418(3) ?, ?? = 97.887(3)°, V = 1939.3(7) ?³, Z = 2. The crystal of II is triclinic: space group P $P\bar 1$ a = 8.334(2), b = 10.236(2), c = 11.337(2) ?, ?? = 80.91(3)°, ?? = 75.41(3)°, ?? = 75.63(3)°, V = 902.0(3) ?³, Z = 2. Complex I is a methoxide-bridged dimeric oxovanadium(V) complex, and complex II is a mononuclear oxovanadium(V) complex. The V atom in I is in an octahedral coordination, and that in II is in a square pyramidal coordination.