Characterization of [Ni(py)4]Cl2 and its thermal decomposition

The stepwise thermal decomposition of [Ni(py)₄]Cl₂ was studied by means of a derivatograph. The stepwise mode of thermal decomposition allowed the preparation of new complexes. X-ray powder diffraction and IR methods were used to study the structures of the decomposition intermediates. [Ni(py)₄]Cl₂ was applied as a model substance. The decompositions of a great number of complex compounds of similar type have been reported, but only a few of them have been investigated structurally by single-crystal X-ray diffraction techniques due to the difficulty of obtaining large single-crystals.

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Zusammenfassung Die schrittweise thermische Zersetzung von [Ni(py)₄]Cl₂ wurde mit einem Derivatographen untersucht. Diese Methode ermöglicht die Darstellung neuer Komplexverbindungen. Zur Untersuchung der Struktur der intermediären Zersetzungsprodukte wurden ebenfalls XPD und IR-Spektroskopie angewandt. [Ni(py)₄]Cl₂ wurde als Modellsubstanz gewählt. Eine große Zahl ähnlicher Komplexverbindungen ist bekannt, aber nur von wenigen wurde die Kristallstruktur wegen der Schwierigkeiten, entsprechend große Einkristalle zu erhalten, durch Einkristall-Röntgendiffraktometrie bestimmt.

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[Ni(py)₄]Cl₄) . . , .

     

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。     

[WS4Cu2（Py）4]的合成及晶体结构

(NH_4)_2WS_4、CuCl和(n-Bu)_4NBr在Ar气氛中,90℃下反应10 h,所得产物先后经CH_2Cl_2与CH_3OH处理,得一桔红色晶体。该晶体与吡啶反应,即得到桔红色针状晶体[WS_4Cu_2(Py)_4],属单斜晶系,空间群C2/c,晶胞参数:a=14.109(1),b=12.704(1),c=14.071(1);β=96.97(1)°;Z=4。结构用重原子法解出,经最小二乘法修正,偏离因子R=0.027。     

Two new [Ni(tren)2]2+ complexes: [Ni(tren)2]Cl2 and [Ni(tren)2]WS4

Both title compounds, bis­[tris(2‐amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2‐amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2‐amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS₄]^2? anion in (II). Hydro­gen bonding is observed in both compounds.     

Electronic structure of Co(III) doped bromo-bridged Ni complexes, [Ni1-xCox(chxn)2Br]Br2

This article describes the electronic structure of the Co(III) doped Br bridged Ni(III) complexes, [Ni(1-x)Cox(chxn)2Br]Br2 (x = 0.01, 0.02, 0.05, and 0.11) by using a optical spectroscopy, scanning tunneling microscopy (STM), and electron spin resonance spectroscopy. In the optical reflectivity spectrum, the new band was formed at about 0.5 eV, which is reasonably recognized as the d(z2) band of doped Co(III) ions. In the STM images of [Ni(1-x)Cox(chxn)2Br]Br2, the bright spots attributable to the tunnel current from the Fermi level of the STM tip to the conduction band of the sample were observed. In addition, some brighter spots were also observed. Because the number of the brighter spots is in good agreement with that of doped Co species, the brighter spots can be assigned to doped Co(III) sites. These are reasonably explained by the tunnel current from the Fermi level of the tip to the d(z2) band of Co(III). The Curie spin concentration was gradually increased with increasing Co(III) ions, which is explained by the scissions of the S = 1/2 1D antiferromagnetic chains.     

配合物[2-NaPhthMePyNH_2]_2[Ni(mnt)_2]的合成及表征

合成了马来二氰基二硫烯镍(Ⅱ)配合物,[2-Na Phth Me Py NH2]2[Ni(mnt)2]([2-Na Phth Me Py NH2]+为1-(2'-萘苄基)-2-氨基吡啶鎓离子),并用元素分析,UV,IR,单晶X-射线衍射表征了其组成和结构。结果表明,配合物系单斜晶系,空间群P21/c,a=13.335(2),b=7.9458(12),c=17.480(3),α=90°,β=97.646(2)°,γ=90°,V=1835.7(5),Z=2。     

Syntheses,Crystal Structures and Non‐linear Optical Properties of Cluster Compounds [MoAu2S4(PPh2Py)2] and [WAu2S4(PPh2Py)2]

The cluster compounds, [MoAu₂S₄(PPh₂Py)₂] ( 1 ) and [WAu₂S₄(PPh₂Py)₂] ( 2 ), were synthesized by the reaction of (NH₄)₂MS₄ (M = Mo, W), H[AuCl₄]·4H₂O and diphenyl‐2‐pyridyl‐phosphine (PPh₂Py) in CH₂Cl₂ solution. [MoAu₂S₄(PPh₂Py)₂] crystallizes in the monoclinic space group P2₁/c with a = 18.385(2), b =12.304(1), c = 16.904(2) Å, β =110.722(2)°, and Z = 4. [WAu₂S₄(PPh₂Py)₂] crystallizes in the triclinic space group P‐1 with a = 9.333 (3), b = 10.628(3), c = 19.566(6) Å, α = 89.26(1), β = 80.87(1), γ = 68.85(1)°, and Z = 2. Single crystal X‐ray analysis showed that these two compounds are isostructural, but belong to different space groups. The Mo (W) atom has a slightly distorted tetrahedral coordination, and the two Au atoms are distorted from trigonal planar, the P—Au—M—Au—P chain is nearly linear. Measurement of the nonlinear optical (NLO) properties using the Z‐scan technique with an 8‐ns pulsed laser at 532 nm showed that 1 and 2 possess NLO absorption and effective self‐focusing effect. The effective α₂ and n₂ values of cluster 1 are 5.89 × 10^—12 m · W^—1 and 6.45 × 10^—18 m² · W^—1; the effective α₂ and n₂ values of compound 2 are 4.35 × 10^—11 m · W^—1 and 3.73 × 10^—17 m² · W^—1.     

On the thermal decomposition of [Ni(H2O)6](NO3)2 and its deuterated analogue

The methods of TG, DTA and DSC were used to study the thermal decompositions of [Ni(H₂O)₆](NO₃)₂ and [Ni(D₂O)₆](NO₃)₂ in an atmospheric air medium. Intermediates were isolated at 145, 230 and 245°, and were identified by quantitative analysis and IR spectroscopy. The following phase transitions were observed under the conditions of the experiment: melting of the salts, partial dehydration to the tetrahydrate, formation of basic nickel nitrate hydrate stable within a narrow temperature interval, and formation of NiO.

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Zusammenfassung Mittels TG, DTA und DSC wurde die thermische Zersetzung von [Ni(H₂O)₆](NO₃)₂ und [Ni(D₂O)₆](NO₃)₂ in Luft untersucht. Bei Temperaturen von T=145°C, 230°C un 245°C konnten Intermediäre festgestellt werden, welche mittels quantitativer Analyse und IR-Spektroskopie identifiziert wurden. Unter den gegebenen experimentellen Bedingungen wurden folgende Phasenumwandlungen beobachtet: Schmelzen der Salze, partielle Dehydratation zu Tetrahydrat, Bildung von basishem Nickelnitrat-hydrat (stabil innerhalb eines schmalen Temperaturintervalles), schließliche Bildung von NiO.Aus den DSC-Daten wurden die Enthalpien der Phasenumwaldungen berechnet. DTA- und DSC-Daten zeigen, daß die Phasenunwandlungen bei [Ni(H₂O)₆](NO₃)₂ bei etwas niedrigeren Temperaturen liegen als bei [Ni(D₂O)₆](NO₃)₂.

     

双金属配合物重铬酸四吡啶合镍(Ⅱ)[Py4Ni(HCrO4)2,TPND]:合成、晶体结构和氧化性质研究

本文合成了双金属配合物重铬酸四吡啶合镍(Ⅱ)[Py4Ni(HCrO4)2,TPND],晶体结构解析表明,TPND是一个以Ni(Ⅱ)为中心的正八面体配合物,而每两个分子之间由两个Ce-O-Cr桥相连接.并对TPND的氧化性质进行了研究,发现其具有很高的脱氢活性,对芳香酮腙的脱氢氧化产率较高(8l%～91%).     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

Nitrosylbromokomplexe des Rheniums: Re(NO)2Br3 und [Re(NO)2Br4]⊖; die Kristallstruktur von PPh4[Re(NO)2Br4] · 2 CCl4

Nitrosyl Bromo Complexes of Rhenium: Re(NO)₂Br₃ and [Re(NO)₂Br₄]^?; Crystal Structure of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ PPh₄[Re(NO)₂Br₄] is prepared in the form of dark red-brown powder by the reaction of PPh₄[Re(NO)₂Cl₄] with excess boron tribromide. From a solution of CH₂Br₂ and CCl₄ it crystallizes with two moles CCl₄, one of which splits off easily in vacuo. The reaction of aluminum tribromide in CH₂Br₂ solution leads to a slightly soluble red-brown Re(NO)₂Br₃ powder. The i.r. spectra indicate cis positions of the covalently bound NO ligands in both complexes. Re(NO)₂Br₃ is dimeric via bromo bridges. The crystal structure determination of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ was solved by X-ray diffraction methods at ? 115°C. The complex crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell (4434 independent reflexions, R = 0.085). The unit cell dimensions are a = 1 092.3 pm, b = 2088.0 pm, c = 1 657.6 pm, β = 96.10°. The structure consists of P(C₆H₅)₄^? cations, [Re(NO)₂Br₄]^? anions and intercalated CCl₄ molecules. In the anion the NO groups are covalently bound to the Re atom like \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm RE}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O} $\end{document} and they are arranged in cis position to one another.     

Synthesis and Structure of Co(III) Coordination Compounds [Co(DH)2(Anil)2][BF4] and [Co(DH)2(Py)2][BF4]

The complex compounds [Co(DH)₂(Anil)₂][BF₄] and [Co(DH)₂(Py)₂][BF₄] were synthesized from Co(BF₄)₂ · 6H₂O–DH₂–A–alcohol–water systems (DH₂ is dimethylglyoxim and A is pyridine (Py) or aniline (Anil)), and their crystal structures were determined using X-ray diffraction analysis. In octahedral Co(III) complexes, two dimethylglyoxime radicals lie in the equatorial plane and are joined via the intramolecular hydrogen bond O–H···O. The complexes with pyridine and aniline have similar configurations but different crystal structures.     

Synthesis and Structural Characterization of the Complex 〔Et_4N〕_2〔Ni_2(C_2S_4)(C_3S_5)_2〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｃｈｅｍｉｓｔｒｙｏｆｃｏｍｐｏｕｎｄｓｗｉｔｈｄｍｉｔ（ｄｍｉｔ＝１,３ ｄｉｔｈｉｏｌｅ ２ ｔｈｉｏｎｅ ４,５ ｄｉｔｈｉｏｌａｔｅ）ｈａｓａｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｅｎｔｉｏｎｒｅｃｅｎｔｌ...     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

Synthesis and Structural Characterization of [Mn（sapn）（H2O）2]Br

1 INTRODUCTION Many of the recent advances in the coordination chemistry of manganese have been driven by the involvement of the manganese in several biological redox-active systems[1,2], of which the most important is the oxygen-evolving complex (EOC) of photosystem II (PS II) in green plants [3]. Since the preparations and structural characterizations of the complexes containing N,O-donor ligands have been studied extensively as simple active-site models for the photosystem II[4,5]…     

Pyridinium‐Chlorometallate von Lanthanoid‐Elementen. Die Kristallstrukturen von [HPy]2[LnCl5(Py)] mit Ln = Eu,Er, Yb und von [H(Py)2][YbCl4(Py)2] · Py

Pyridinium Chlorometallates of Lanthanoid Elements. Crystal Structures of [HPy]₂[LnCl₅(Py)] mit Ln = Eu, Er, Yb und von [H(Py)₂][YbCl₄(Py)₂] · Py The pyridinium chlorometallates [HPy]₂[LnCl₅(Py)] with Ln = Eu, Er and Yb, as well as [H(Py)₂][YbCl₄(Py)₂]·Py have been obtained by the reaction of diacetone alcohol with solutions of the corresponding metal trichlorides in pyridine at 100 °C. According to the crystal structure determinations the anions [LnCl₅(Py)]^2— are linked by bifurcated Cl···H···Cl bridges with the protons of the [HPy]⁺ cations forming chains along [001]. The anions of [H(Py)₂][YbCl₄(Py)₂]·Py form discrete octahedrons with trans‐positions of the pyridine ligands. [HPy]₂[EuCl₅(Py)] ( 1a ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1874.4(2), b = 1490.2(2), c = 741.5(1) pm, R₁ = 0.0466. [HPy]₂[ErCl₅(Py)] ( 1b ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1864.3(1), b = 1480.7(2), c = 739.7(1) pm, R₁ = 0.0314. [HPy]₂[YbCl₅(Py)] ( 1c ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1858.9(2), b = 1479.0(1), c = 736.8(1) pm, R₁ = 0.0306. [H(Py)₂][YbCl₄(Py)₂]·Py ( 2 ·Py): Space group Ia, Z = 4, lattice dimensions at —80 °C: a = 1865.5(1), b = 827.5(1), c = 1873.4(1) pm, ß = 103.97(1)°, R₁ = 0.0258.     

Tetracyanometallates with Complex Dien Cations: [Ni(dien)2][Ni(CN)4]·2H2O and [Ni(dien)2][Pd(CN)4]

The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)₂][Ni(CN)₄]·2H₂O (NDNCH) and [Ni‐(dien)₂][Pd(CN)₄] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)₂]²⁺ cations and [Ni(CN)₄]^2‐ or [Pd(CN)₄]^2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)₂][Ni(CN)₄] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.     

Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2

Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr₂(NPMe₃)]₂, [B₂Br₃(NPⁱPr₃)₂]Br, [B₂(NPEt₃)₄]Br₂, [B₂Br₂(NPPh₃)₃]BBr₄ and [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me₃SiNPR₃ and boron tribromide. The boron subcompound [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl₂ derives from Me₃SiNPEt₃ and B₂Cl₂(NMe₂)₂. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr₂(NPMe₃)]₂ (1): Space group P2₁/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ₂-N bridges of the NPMe₃^? groups of from B₂N₂ four-membered rings with B? N distances of 149.9 and 150.9 pm. B₂Br₃(NPⁱPr₃)₂]Br (2): Space group P2₁, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ₂-N atoms of the NPⁱPr₃^? groups to form planar, asymmetric B₂N₂ four-membered rings with B? N distances of 143 and 156 pm. [B₂(NPEt₃)₄[Br₂·4CH₂Cl₂ (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt₃^? groups to form a B₂N₂ four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt₃^? groups are terminally bonded with very short B? N distances of 133.5 pm. B₂Br₂(NPPh₃)₃]BBr₄ (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ₂-N atoms of two of the NPPh₃^? groups to form a nearly planer B₂N₂ four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh₃³ group is terminally connected with teh sp² hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B₂(NMe₂)₂}₂(NPEt₂)₂]Cl₂ · 3CH₂Cl₂ (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ₂-N atoms of the two NEPt₃^? groups to form B₄N₂ six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe₂^? groups correspond to 138 pm double bonds.     

Activation energy of thermal decomposition of LaC2O4Br

The activation energy of the thermal decomposition of finely ground LaC₂O₄Br was determined according to the method of Ozawa asE _a=203.83 kJ mol^?1. As compared to the value for the parent oxalate La₂(C₂O₄)₃ E _a=130 kJ/mol), this value is higher by about 70 kJ/mol, which is consistent with the increased interaction between the metal and oxalate ions. The substitution of Br by Cl does not affect the decomposition kinetics profoundly.     

Synthese und Kristallstrukturen von (PPh4)2[As2Se4Cl12] und (PPh4)2[As2Se4Br12]

Synthesis and Crystal Structures of (PPh₄)₂[As₂Se₄Cl₁₂] and (PPh₄)₂[As₂Se₄Br₁₂] The reaction of PPh₄Cl and As₂Se₃ with SOCl₂ or with chlorine in dichloromethane affords (PPh₄)₂[As₂Se₄Cl₁₂] with good yields. From PPh₄Br, As₂Se₃ and bromine the corresponding bromo compound was obtained. According to the X-ray crystal structure determinations both compounds are isotypic, crystallizing in the space group of P1 . In the anions two Se₂X₂ molecules are linked with two X^? ions forming an Se₄X₂ ring in chair conformation. Each X^?-ion is associated with an additional AsX₃ molecule (X = Cl, Br).