Hexacyanocobaltate(III) anions as precursors of Co(II)-Ni(II) cyano-bridged multidimensional assemblies: hydrothermal syntheses, crystal and powder X-ray structures, and magnetic properties

Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by two chelating 2,2'-bipy ligands and two cyanides from two different [Ni(CN)4]2- units cis to each other. These compounds have been fully characterized by single-crystal or unconventional powder X-ray diffraction analyses and variable-temperature magnetic measurements.     

Studies of a series of [Ni(P(R)2N(Ph)2)2(CH3CN)]2+ complexes as electrocatalysts for H2 production: substituent variation at the phosphorus atom of the P2N2 ligand

A series of [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes containing the cyclic diphosphine ligands [P(R)(2)N(Ph)(2) = 1,5-diaza-3,7-diphosphacyclooctane; R = benzyl (Bn), n-butyl (n-Bu), 2-phenylethyl (PE), 2,4,4-trimethylpentyl (TP), and cyclohexyl (Cy)] have been synthesized and characterized. X-ray diffraction studies reveal that the cations of [Ni(P(Bn)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) and [Ni(P(n-Bu)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) have distorted trigonal bipyramidal geometries. The Ni(0) complex [Ni(P(Bn)(2)N(Ph)(2))(2)] was also synthesized and characterized by X-ray diffraction studies and shown to have a distorted tetrahedral structure. These complexes, with the exception of [Ni(P(Cy)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2), all exhibit reversible electron transfer processes for both the Ni(II/I) and Ni(I/0) couples and are electrocatalysts for the production of H(2) in acidic acetonitrile solutions. The heterolytic cleavage of H(2) by [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes in the presence of p-anisidine or p-bromoaniline was used to determine the hydride donor abilities of the corresponding [HNi(P(R)(2)N(Ph)(2))(2)](BF(4)) complexes. However, for the catalysts with the most bulky R groups, the turnover frequencies do not parallel the driving force for elimination of H(2), suggesting that steric interactions between the alkyl substituents on phosphorus and the nitrogen atom of the pendant amines play an important role in determining the overall catalytic rate.     

4,2-Ribbon like ferromagnetic cyano-bridged Fe(III)2Ni(II) chains: a magneto-structural study

The low-spin iron(III) complex AsPh(4)[Fe(III)(bpy)(CN)(4)].CH(3)CN (1) [AsPh(4) = tetraphenylarsonium cation] and the heterobimetallic chains [{Fe(III)(L)(CN)(4)}(2)Ni(II)(H(2)O)(2)].4H(2)O with L = bpy (2) and phen (3) [bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline] have been prepared and their structures determined by X-ray diffraction methods. The structure of 1 consists of mononuclear [Fe(bpy)(CN)(4)](-) anions, tetraphenylarsonium cations and acetonitrile molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of the bidentate bpy and four carbon atoms of four terminal cyanide groups building a distorted octahedral surrounding around the metal atom. 2 and 3 are isomorphous compounds whose structure is made up of neutral 4,2-ribbon like bimetallic chains of formula [{Fe(III)(L)(CN)(4)}(2)Ni(II)(H(2)O)(2)] where the [Fe(III)(L)(CN)(4)](-) unit acts as a bis-monodentate bridging ligand toward the trans-diaquanickel(II) units through two of its four cyanide groups in cis positions. The chains exhibit two orientations in the unit cell and they interact with each other through hydrogen bonds involving the coordination and crystallization water molecules together with the uncoordinated cyanide nitrogen atoms of the [Fe(L)(CN)(4)](-) units. Compounds 2 and 3 behave as ferromagnetic Fe(III)(2)Ni(II) chains which interact ferromagnetically at very low temperatures in the case of 2, whereas metamagnetic-like behaviour is observed for with a critical field (H(c)) around 200 G. For H > H(c) the ferromagnetic Fe(III)(2)Ni(II) chains of 3 exhibit a frequency dependence of the out-of-phase ac susceptibility signal at T < 3.5 K.     

Synthesis and Structure of Cobalt(III) Complex with Cyanomethylene and N,N′-Ethylenebis(3-methylsalicylideneiminate)

Russian Journal of General Chemistry - The new complex [CoIII(3-CH3Salen)(CH2CN)]·CH3CN was synthesized and its crystal structure was determined by the X-ray diffraction analysis. The...     

Oxygen reactivity of a nickel(II)-polyoximate complex

The ligand tris(2-hydroxyiminopropyl)amine (Ox(3)H(3)) binds to nickel(II) in multiple protonation states. In the neutral state, the X-ray crystal structure of the monomeric complex [Ni(Ox(3)H(3))(NO(3))(H(2)O)](NO(3)).(H(2)O), 1, has six-coordinate pseudo-octahedral geometry, with binding of the amine and three oxime nitrogens, a nitrate, and a water. In the mono-deprotonated form, the X-ray crystal structure shows a dimer, [Ni(Ox(3)H(2))(CH(3)CN)](2)(ClO(4))(2), 2, which has bridging oximate groups and a Ni-Ni distance of 3.575 A. The fully deprotonated complex, 3, shows significantly low Ni(II) oxidation potentials at -390 and +165 mV (versus Fc(+)/Fc). Complex 3 shows reactivity when exposed to O(2), consuming multiple O(2) equivalents and turning from the purple 3 to a dark brown complex, 4. Complex 4 has an EPR spectrum consistent with Ni(III), but spin quantitation accounts for only about 10% of the total Ni, consistent with turnover of the Ni oxidation states. This Ni(II)/O(2) system oxidizes triphenylphosphine to its oxide, with incorporation of the isotopic label from O(2).     

一种含[Ni(CN)4]2-和[Cu(pn)]2+构筑元组成的超分子配合物的合成、单晶结构和磁学性质

A cyano-bridged heterometallic supramolecular complex {[Cu(pn)]₃[Ni(CN)₄]₃}_n (1) has been synthesized and structurally characterized by single crystal X-ray diffraction. 1 displays an interesting 3D structure formed by μ₄, μ₃-[Ni(CN)₄]^2- tectons bridging five-coordinated and six-coordinated Cu(II) ions. The magnetic property shows that 1 behaves as weakly ferromagnetic interactions between the adjacent Cu(II) ions through the diamagnetic spacer NC-Ni-CN. CCDC: 624387.     

Different nuclearity silver(I) complexes with novel tetracyano pendant-armed hexaazamacrocyclic ligands

A new series of different nuclearity silver(I) complexes with a variety of tetracyano pendant-armed hexaazamacrocyclic ligands containing pyridine rings (Ln) has been prepared starting from the nitrate and perchlorate Ag(I) salts in acetonitrile solutions. The ligands and complexes were characterized by microanalysis, conductivity measurements, IR, Raman, electronic absorption and emission spectroscopy, and L-SIMS spectrometry. (1)H NMR titrations were employed to investigate silver complexation by ligands L3 and L.(4) The compounds [Ag2L2(NO3)2] (2), ([Ag2L2](ClO4)2.2CH3CN)(infinity) (4), [AgL3](ClO(4)).CH3CN (5), and [Ag4(L4)2(NO3)2](NO3)2.4CH3CN.2H2O (7) were also characterized by single-crystal X-ray diffraction. The complexes have different nuclearities. Complex 2 is dinuclear with an {AgN3O2} core and a significant intermetallic interaction, whereas complex 4 has a polymeric structure formed by dinuclear distorted {AgN4} units joined by nitrile pendant arms. Compound 5 is mononuclear with a distorted {AgN2} linear geometry, and complex 7 consists of discrete units of a tetranuclear array of silver atoms with {AgN3O} and {AgN4} cores in distorted square planar environments. Complexes 2 and 4 were found to be fluorescent in the solid state at room temperature because of the Ag-Ag interactions.     

Synthesis,Crystal Structure,and Catalytic Performance of 2,6-Bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine Nickel(Ⅱ)Complex

A novel nickel(Ⅱ) complex Ni[L]Cl2·CH3CN(1) containing the tridentate ligand 2,6-bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine(L) has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane(MAO).     

Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis

Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) ?) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) ?) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) ?) is shorter than the Ni-N(py) bond (2.074(4) ?) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed.     

Coordination chemistry of amine bis(phenolate) cobalt(II), nickel(II), and copper(II) complexes

Cobalt(II), nickel(II), and copper(II) (1, 2, and 3) complexes of the dianionic form of the bis(phenolate) ligand N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H2L) have been synthesized by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the ligand. When copper is used as the anode, the addition of 1,10-phenanthroline to the electrolytic phase gave rise to a different compound [CuL]2.2CH3CN (4). The compounds [CoL]2.2CH3CN (1), [Ni2L2(H2O)].H2O (2), [CuL]2.3H2O (3), and [CuL]2.2CH3CN (4) were characterized by microanalysis, IR, electronic spectroscopy, FAB mass spectrometry, magnetic measurements and by single-crystal X-ray diffraction. The crystal structures show that the complexes have a dinuclear structure. In compounds 1, 3, and 4, two metal ions are coordinated by the two amine nitrogens and the two phenol oxygen atoms of a deprotonated pendant phenol ligand, with one phenolic oxygen atom from ligand acting as a bridge. In compounds 1 and 3, each metal center has a geometry that is closest to trigonal bipyramidal. Magnetic susceptibility data for both compounds show an antiferromagnetic coupling with 2J = -15 cm(-1) for the cobalt(II) complex and a strong antiferromagnetic coupling with 2J = -654 cm(-1) for the copper(II) complex. However, in 4 the geometry around the metal is closer to square pyramidal and the compound shows a lower antiferromagnetic coupling (2J = -90 cm(-1)) than in 3. The nickel atoms in the dimeric compound 2 are hexacoordinate. The NiN2O4 chromophore has a highly distorted octahedral geometry. In this structure, a dianionic ligand binds to one nickel through the two amine nitrogen atoms and the two oxygen atoms and to an adjacent nickel via one of these oxygen atoms. The nickel atoms are linked through a triple oxygen bridge involving two phenolic oxygens, each from a different ligand, and an oxygen atom from a water molecule. The two nickel ions in 2 are ferromagnetically coupled with 2J = 19.8 cm(-1).     

Syntheses, structures, spectroscopy, and chromotropism of new complexes arising from the reaction of nickel(II) nitrate with diphenyl(dipyrazolyl)methane

The complexes [(dpdpm)Ni(2-NO3)2] (1), [(dpdpm)Ni(2-NO3)(1-NO3)(CH3CN)] (2), [(dpdpm)2Ni(1-NO3)(H2O)]NO3 (3), and [(dpdpm)2Ni(H2O)2][NO3]2 (4) (dpdpm = diphenyl(dipyrazolyl)methane, Ph2C(C3N2H3)2), have been prepared and characterized by IR and UV-vis-NIR spectroscopy and X-ray diffraction studies. X-ray studies have confirmed that complexes 1-4 all adopt variously distorted octahedral structures in the solid state, the largest distortions arising from the small bite-angle of the bidentate nitrate ligand in 1 and 2. Magnetic moment measurements indicate that these solids are paramagnetic with two unpaired electrons. The solution 1H NMR data show that the paramagnetism is maintained in solution. Absorption spectra of 1-4 show three main bands in the region of 350-1000 nm representing spin allowed (d-d) transitions from the ground state 3A2g to the excited states 3T2g, 3T1g(3F), and 3T1g(3P). A weak shoulder was also detected at about 700-800 nm in most spectra, representing spin-forbidden transitions 3A2g 1Eg. A comparison of the crystal field parameters 10Dq and B for 1-4 to the corresponding values for related complexes indicated that these parameters are fairly insensitive to structural variations within this family of complexes. The 10Dq/B ratios show greater variations, but no clear correlations are apparent between 10Dq/B and such structural features as the nature of ligator atoms (N:O ratio), the bonding mode of the nitrate ligand, or the overall charge. Complexes 1 (green) and 2 (blue) interconvert as a function of temperature (solutions and solid samples), concentration of CH3CN (solutions), or CH3CN vapor pressure (solid samples).     

Metal-catalysed oxidation processes in thiosemicarbazones: new complexes with the ligand N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide

The coordination behaviour of a new thiosemicarbazone Schiff-base building block, N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide, H2L1 (1), incorporating a bulky tosyl group, towards Mn II, Fe II, Co II, Ni II, Cu II, Zn II, Cd II, Ag I, Sn II, and Pb II has been investigated by means of an electrochemical preparative procedure. Most metal complexes of L1 have the general formula [M(L1)]2.nX (M=Mn, Fe, Co, Ni, Cu, Cd, Pb; n=0-4, X=H2O or CH3CN), as confirmed by the structure of [Pb(L1)]2 (15), in which the lone pair on lead is stereochemically active. This lead(II) complex shows an intense fluorescence emission with a quantum yield of 0.13. In the case of silver, the complex formed was found to possess a stoichiometry of [Ag2(L1)]2.3H2O. During reactions with manganese and copper metals, interesting catalysed processes have been found to take place, with remarkable consequences regarding the ligand skeleton structure. In synthesising the manganese complex, we obtained an unexpected dithiolate thiosemicarbazone tosyl ligand, H2L2, as a side-product, which has been fully characterised, including by X-ray diffraction analysis. In the case of copper, the solid complex has the formula [CuL1]2, but the crystallised product shows the copper atoms coordinated to a new cyclised thiosemicarbazone ligand, H2L3, as in the structures of the complexes [Cu(L3)]2.CH3CN (8) and [Cu(L3)(H2O)]2.CH3CN.H2O (9). The zinc complex [Zn(L1)]4 (12) displays a particular tetranuclear zeolite-type structure capable of hosting small molecules or ions, presumably through hydrogen bonding.     

Pd2L2 metallacycles as molecular containers for small molecules

M(2)L(2) type metallacyclic complexes, [Pd(2)(L1)(2)Cl(4)]·1.5CH(2)Cl(2) (1), [Pd(2)(L1)(2)Cl(4)]·2CHCl(3) (2), [Pd(2)(L2)(2)Cl(4)]·2CH(2)Cl(2)·2CH(3)CN (3), [Pd(2)(L2)(2)Cl(4)]·2CHCl(3)·2CH(3)CN (4) and [Pd(2)(L3)(2)Cl(4)]·CH(2)Cl(2)·2CH(3)CN (5), have been prepared from three semi-rigid benzimidazol or benzotriazol ligands, 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L2) and 1,4-bis(benzotriazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L3). All the complexes were structurally characterized by single-crystal X-ray diffraction and the phase purity was confirmed by powder X-ray diffraction (PXRD) measurements. The solution structure of representative complex 1 was studied by (1)H NMR titration and ESI mass spectroscopy. The thermal stability and guest-exchange properties of 1, 3 and 4 were investigated, revealing that the Pd(2)L(2) metallacycles can act as a selective receptor for CH(2)Cl(2) or CHCl(3) guest molecules. The catalytic activity of 1 in Suzuki-Miyaura coupling reaction was also studied and 1 could be recycled at least 5 times under heterogeneous conditions, indicative of a potential self-supported catalyst.     

Neutron diffraction and theoretical DFT studies of two dimensional molecular-based magnet K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O

Exchange mechanisms and magnetic structure in the two-dimensional cyano-bridged molecule-based magnet K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O have been investigated by a combination of neutron diffraction studies on both single crystal and powder samples and theoretical DFT calculations. The experimental spin density has been deduced from a new refinement of previously obtained polarized neutron diffraction (PND) data which was collected in the ordered magnetic state at 4 K under a saturation field of 3 T performed in the C2/c space group, determined by an accurate re-evaluation of the X-ray structure. Positive spin populations were observed on the two manganese sites, and negative spin populations were observed on the molybdenum site, which provides evidence of antiferromagnetic Mo3+-Mn2+ exchange interactions through the cyano bridge. The experimental data have been compared to the results of DFT calculations. Moreover, theoretical studies reveal the predominance of the spin polarization mechanism in the Mo-C-N-Mn sequence, with the antiferromagnetic nature of the interaction being due to the overlap between the magnetic orbitals relative to manganese and molybdenum in the cyano bridging region. The magnetic structure of K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O has been solved at low temperature in zero field by powder neutron diffraction measurements. The structure was found to be ferrimagnetic where the manganese and molybdenum spins are aligned along the axis in opposite directions.     

Synthetic Strategies To Obtain V-P-O Open Frameworks Containing Organic Species as Structural Directing Agents. Crystal Structure of the V(IV)-Fe(III) Bimetallic Phosphate [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)][Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O

A general synthetic approach to rationalize the solution preparative chemistry of oxovanadium phosphates containing organic species as structural directing agents is presented. Careful attention is payed to the hydrolysis and condensation processes involving the ionic species in solution, and a simple restatement of the partial charge model (PCM) has been used in order to organize the experimental results. The structure of a new V(IV)-Fe(III) bimetallic oxovanadium phosphate, [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)] [Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O, has been determined by X-ray single crystal diffraction methods. This compound crystallizes in the monoclinic system, space group P2(1)/n and the cell dimensions are as follows: a = 14.383(3) ?, b = 10.150(2) ?, c = 18.355(4) ?, and beta = 90.39(3) degrees (Z = 2). The existence of a complex intercrossing channel system, including a very large channel of 18.4 ? of diameter (in which both water molecules and ethylenediamine species are located), is the more interesting feature of this structure. Thermal decomposition, including the dehydration/rehydration process, has been studied by thermal analysis and variable temperature X-ray powder diffraction techniques. A complementary SEM study of the different intermediate decomposition products is presented.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-SPh) (μ-SCH2CH2CN)Fe_2 (CO)_6

<正> The crystal and molecular structure of (μ-SPh)(μ-SCH2CH2CN)Fe2-(CO)5 has been determined by X-ray diffraction method. The crystals of this complex are triclinic, space group P1,with a=ll.175(1), b=ll.877(2), c= 15.640(2)1,α=106.20(1),β=103.15(1),γ=98.46(1)°; Z=4; Dc=1.67g/cm3. The final structure refinement converged with unweighted and weighted R factors of 0.028 and 0.034 for 2853 observed unique reflections.     

配位聚合物[Ni(Hsal)2(Py)2]n(Hsal=水杨酸根,Py=吡啶)的合成,表征和晶体结构

用水杨酸和吡啶与Ni(ClO4)26H2O 合成了一个新颖配位聚合物[Ni(Hsal)2(Py)2]n。对配合物进行了X射线衍射结构表征, C24H20N2NiO6, Mr = 491.13, 晶体属三斜晶系, P 空间群, 晶胞参数: a = 7.372(2), b =10.852(2), c = 14.728(3) ? a = 108.36(3), b = 93.83(3), g = 103.67(3), V = 1073.7(4) ?。F(000) = 508, m = 0.949mm-1, Z = 2, Dc = 1.519 g/cm3。最后修正到R = 0.0390, wR = 0.0772。配合物中Ni为五配位, 呈四方锥构型。配合物中2个水杨酸根的配位方式不一样, 其中一个水杨酸根作为双齿桥连配体, 使配合物呈一维链状结构。水杨酸苯环的-堆积作用和分子间的氢键作用, 又使配合物呈二维网络结构。     

Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ complexes

[Ni(P(R)(2)N(R')(2))(2)(CH(3)CN)](2+) complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P(R)(2)N(R')(2))(P(R'(2))N(R'(2)))(CH(3)CN)](2+) with R = Cy, R' = Ph, R' = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO(2), protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ～0.04 M (34 equiv). At concentrations above ～0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η(1)-OC(O)CH(3) binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO(2) liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.     

Heterometallic MIIRuIII2 compounds constructed from trans-[Ru(Salen)(CN)2]- and trans-[Ru(Acac)2(CN)2]-. Synthesis, structures, magnetic properties, and density functional theoretical study

The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N'-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}.6CH3OH.2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn(II) and Ru(III) centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2.H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}.2CH3OH.2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru(III) and M(II) (Mn(II), Ni(II)) ions.     

Ge(7)O(13)(OH)(2)F(3)](3)(-).Cl(-).2[Ni(dien)(2)](2+): the first chainlike germanate templated by a transition metal complex

The first chainlike germanate, [Ge(7)O(13)(OH)(2)F(3)](3)(-).Cl(-).2[Ni(dien)(2)](2+), has been solvothermally synthesized by using Ni(dien)(2)(2+) cations as the template and characterized by IR, SEM, TGA, powder X-ray diffraction (PXRD), energy-dispersive X-ray analysis (EDXA), elemental analysis, and single-crystal X-ray diffraction, respectively. This compound crystallized in the monoclinic space group P2/nwith a = 8.8904(2) A, b = 17.4374(3) A, c = 13.2110(3) A, beta = 101.352(1) degrees, V = 2007.97(7) A(3), and Z = 2. Interestingly, the structure contains two types of chiral mer-[Ni(dien)(2)](2+) cations and two types of chiral chains, one left-handed and the other right-handed, which lead to a racemic compound. The orderly separation of achiral s-fac-[Ni(dien)(2)](2+) and chiral mer-[Ni(dien)(2)](2+) isomers was found in the structure. The structure is stabilized by N-H.O(F, Cl) hydrogen bonds.