New polynuclear molecular ferromagnetic complex {Co3((η2-NH2)2C6H2Me2)2(μ-OOCCMe3)2(η1-OOCCMe3)2(η2-OOCCMe3)2(HOOCCMe3)2}{Co((η2-NH2)2C6H2Me2)2(η1-OOCCMe3)2}

Russian Chemical Bulletin -     

1,2,4-Triphospholyl gold(I) and copper(I) complexes: synthesis,crystal and molecular structures of [Cu(PMe3)2(μ-P3C2tBu2)(μ-I)Cu(PMe3)2], [Cu(PMe3)2(μ-P3C2tBu2)2Cu(PMe3)2] and [Au(η1-P3C2tBu2)2][Au(PEt3)2]

Treatment of K(P₃C₂^tBu₂) with Cu₂I₂ and PMe₃ gave the binuclear complex [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)₂Cu(PMe₃)₂] via the isolated intermediate compound [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)(μ-I)Cu(PMe₃)₂]. The reaction of K(P₃C₂^tBu₂) with [AuCl(PEt₃)] on the otherhand gave the cation:anion complex [Au(PEt₃)₂][Au(η¹-P₃C₂^tBu₂)₂]. All complexes were fully characterised by multinuclear spectroscopy and single crystal X-ray diffraction studies.     

STRUCTURAL STUDIES OF THE COPPER(II) ACETATE COMPLEXES Cu(o2CCH3)2(pyridine)3 AND Cu6(μ-O2CCH3)4(μ4-O2CCH3)2(μ-OCMe3)6

Abstract

[Cu(O₂CCH₃)₂]₂, 1, reacts with pyridine to form violet-blue Cu(O₂CCH₃)₂(pyridine)₃, 2, in > 90% yield. 2 crystallizes from pyridine with a distorted square-pyramidal geometry around copper with the monodentate acetate ligands located diagonally in the basal positions. 1 reacts with Bi(OCMe₃)₃ in THF to form blue Cu₆(μ-O₂CCH₃)₄(μ₄-O₂CCH₃)₂(μ-OCMe₃)₆, 3. 3 crystallizes from THF/hexanes with a hexagon of copper atoms linked by six doubly-bridging tert-butoxide ligands, four doubly-bridging bidentate acetates, and two quadruply-bridging bidentate acetate ligands.     

Synthesis and Structure of [Pd(NH3)4][cis-Pd(NH3)2(SO3)2][Pd(NH3)3(SO3)] · H2O

A new palladium compound [Pd(NH₃)₄][cis-Pd(NH₃)₂(SO₃)₂][Pd(NH₃)₃(SO₃)] · H₂O (I) was synthesized and its structure was studied by X-ray powder diffraction method. In the course of the synthesis, the initial trans-diamminesulfite anionic complex is transformed into the cis-configuration. Further heating in aqueous solution results in isomerization of a substance into a neutral complex [Pd(NH₃)₃(SO₃)]. Crystals I are triclinic: a = 10.3297(2) Å, b = 14.1062(3) Å, c = 6.8531(1) Å, = 101.36(0)°, = 92.74(0)°, = 92.71(0)°, space group P1¯. Structure I consists of the columns with alternating cis-[Pd(NH₃)₂(SO₃)₂]^2– and [Pd(NH₃)₃(SO₃)] complexes and [Pd(NH₃)₄]²⁺ ions between the columns.     

(Me3Si)2NBCl2和(Me3Si)2NB(Cl)NHSiMe3的合成及其成环反应

自从氮化硼陶瓷纤维用聚合物先驱体法[1]合成以后,硼氮六元环化合物越来越为人们所重视[2],文中在制备氮化硼纤维先驱体的过程中,合成了其中间产物,通过热缩合成环反应,合成了含有硼氮六员环的化合物,并采用色-质联用技术对其进行了表征。1　实验部分参照文献[3],改用液氮和丙酮为冷冻剂,控制温度在-50到-40℃,搅拌下向三氯化硼的正戊烷溶液中缓慢滴加三乙胺的正戊烷溶液,滴完后Ｎ2气氛下-50℃加丙酮冷凝回流2ｈ,慢慢由-50℃升至室温,抽滤即得到白色产物Ｅｔ3ＮＢＣｌ3(Ａ)。将Ａ溶于适量苯中[4,5],加入等物质的量的三乙胺,加热回流搅拌…     

N,N-二乙基氨荒酸铋化合物(Et2NCS2)2(NO3)Bi(NO3)-Bi(S2CNEt2)2(HOCH3)的合成及晶体结构

利用硝酸铋和N,N-二乙基氨荒酸盐反应,合成了新型铋的N,N-二乙基氨荒酸衍生物(Et2NCS2)2(NO3)Bi(NO3)Bi-(S2CNEt2)2(HOCH3).通过元素分析和红外光谱对其结构进行了表征.用X射线单晶衍射测定了该化合物的分子和晶体结构.结果表明,化合物的晶体为三斜晶系空间群P1,晶胞参数:a=0.9880(3)nm,b=1.2778(3)nm,c=3.1993(9)nm,α=89.888(4)°,β=85.728(4)°,γ=89.824(4)°,Z=4,V=4.0277(19)nm3,Dc=1.925 g/m3,μ=9.183 mm-1,F(000)=2248,R1=0.0525,wR2=0.0546.该化合物中存在2个不同的铋原子,它们分别为配位数7和8的畸变五角双锥和十二面体构型.在晶体中,通过相邻分子间的S…S弱相互作用和氢键作用,形成了一维链状结构.     

Ru(bipy)_3~(2+)-CO_3~(2-)-SO_3~(2-)-KClO_3体系化学发光法测定空气中的二氧化硫

提出了 Ru(bipy) 2 +3 - CO2 -3 - SO2 -3 - KCl O3 体系化学发光法测定溶液中亚硫酸盐的方法。SO2 -3 浓度与化学发光强度在 1 .0× 1 0 - 7～ 1 .0× 1 0 - 4mol/L 范围内成正比 ,检出限为 8.76× 1 0 - 8mol/L,对 1 .0× 1 0 - 4mol/L SO2 - 3 溶液 6次测定的相对标准偏差为 2 .9%。该法用三乙醇胺作为吸收液 ,成功地用于测定空气中二氧化硫的含量 ,结果满意。     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

SYNTHESIS AND CHARACTERIZATION OF (PPh_3)_3Co(μ-CO)_2 V(CO)_2Cp AND (PPh_3)

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ（ＰＰｈ_３）_３Ｃｏ（μ－ＣＯ）_２Ｖ（ＣＯ）_２ＣｐＡＮＤ（ＰＰｈ_３）ＨＰｔ（μ－ＣＯ）（μ－ＰＰｈ_２）Ｖ（ＣＯ）_２ＣｐＣｈａｎｇＰｉｎｇＳＨＡＯ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈ?..     

Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.     

STRUCTURAL EVIDENCES OF Ru (H)_2(H_2) (PPh_3)_3 AT LOW TEMPERATURE

FTIR spectrum at liquid nitrogen temperature and IH NMR ofair-sensitive polyhydride Ru(H)_2(H_2)(PPh_3)_3 have been measured for the firsttime. It is found that a fluxional process happens at room temperature, butthe structure of Ru(H)_2(H_2)(PPh_3)_3 with non-equivalent hydrogens isdiscernible at low temperature.     

Reactions of the Cluster Anion [HRu3(CO)11)]− with Dicyclohexylphosphine: Synthesis and Molecular Structure of H2Ru3(CO)8(PCy2)2 and H2Ru3(CO)6(PCy2)2(HPCy2)2

The cluster anion [HRu₃(CO)₁₁]^- (1) reacts with dicyclohexylphosphine in THF solution to give the anionic derivative [HRu₃(CO)₈(PCy₂)₂]^- (2), protonation of which yields the neutral cluster H₂Ru₃(CO)₈(PCy₂)₂ (3) and, in the presence of excess phosphine, HRu₃(CO)₇(PCy₂)₃ (4). In protic methanol as reaction medium, the reaction of 1 with HPCy₂ gives directly the neutral complex H₂Ru₃(CO)₆(PCy₂)₂(HPCy₂)₂ (5), together with 4. The single-crystal structure X-ray analysis of 3 shows a closed triangular Ru₃ framework. The electron count is in accordance with the EAN rule, but the structure analysis of 5 reveals an open, almost linear Ru₃ skeleton, which is electron-deficient with respect to the EAN rule.     

Crystal structure of Μ2, η2, Σ2-nitrato-η2, Σ2-nitrato-bis(1-ethyltetrazole-N4)copper(II) Cu(C3H6N4)2(NO3)2 = [Cu(C3H6N4)2(NO3)(NO3)2/2]∞

The complex compound of copper(II) nitrate with 1ethyltetrazole (ettz), Cu( C₃H₆N₄)₂(NO₃)(NO₃)_2/2] is studied by Xray diffraction analysis (“Syntex P2₁” automatic diffractometer, CuK_a radiation, graphite monochromator, 6/26 scan mode with V_min = 3.91 deg/min, the total number of data collected 3544 l_hkb including 3141 nonextinct l_hkl > 0, a correction for absorption (Μ = 25.08 cm^-1) applied by integrating over the crystal faces). The parameters of the orthorhombic unit cell (space group Pccn) are a = 15.436(3), b = 20.198(5), c = 19.587(3) Å, V_cell = 6107(2) Å^{3, Z} = 16, d_calc = 1.670 g/cm³. The two crystallographically independent copper atoms have a distorted octahedral environment (coordination node is CuN₂O₄), coordination number (CN) is 6 = 4 + t2. In the equatorial plane, two nitrogen atoms of ettz and two oxygen atoms of NO ₃ ^? groups are trans to each other; Cu-N = 1.983(8), C-O_{NO 3} ^? = 1.978(7) Å (average). The nitrato groups fulfill chelate and bridging functions, complementing the coordination polyhedra of the copper atoms to distorted octahedra, where Cu-O_{NO 3} ^? = 2.517(7) Å (average). The compound has a chain structure; the chains stretching along [001] are packed pairwise according to the hexagonal law.     

Synthesis and structure of [Cr3O(CH3COO)6(H2O)3][UO2 (CH3COO)3] · 3H2O

Crystals of [Cr₃O(CH₃COO)₆(H₂O)₃][UO₂(CH₃COO)₃]·3H₂O (I) were synthesized for the first time and studied by X-ray crystallography. The crystals of I are orthorhombic: a = 8.3561(3) ?, b = 16.8421(5) ?, c = 25.7448(9) ?, V = 3623.2(2) ?³, space group P2₁2₁2₁, Z = 4, R = 0.0409. The structure is composed of trinuclear [Cr₃O(CH₃COO)₆(H₂O)₃]⁺ complexes and mononuclear [UO₂(CH₃COO)₃]^? complexes classified with crystal-chemical groups A₃M³B ₆ ² M ₃ ¹ (A = Cr³⁺, M³ = O^2?, B² = CH₃COO^?, M¹ = H₂O) and AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?), respectively. The complexes are bound to each other by electrostatic interactions and hydrogen bonds involving outer-sphere water molecules. The results of IR spectroscopic study of I are in good agreement with the structural data for the crystal.     

Fe(CO)_3(PR_3)_2和Fe(CO)_2(PR_3)_3的结构与性质的理论研究

采用B3LYP和BP86方法,对铁羰基衍生物Fe(CO)_3(PR_3)_2和Fe(CO)_2(PR_3)_3(R=Cy,OPh和Ph)的几何和电子结构、成键特点以及热力学稳定性等进行了理论研究.计算结果表明,Fe(CO)_3(PR_3)_2的基态结构都为三角双锥的轴向双取代;对于Fe(CO)_2(PR_3)_3来说,三角双锥的腰部三取代(D_(3h))和腰部+轴向双取代(C_(2v))结构能量差别非常小.自然键轨道(NBO)分析显示,膦配体向羰基铁基团存在电荷转移,使得Fe—CO之间的共价作用有效增强.含膦配体铁羰基化合物Fe(CO)_3(PR_3)_2的第一膦配体解离能比第一羰基解离能低,预示Fe(CO)_3(PR_3)_2的反应活性比Fe(CO)_5有明显提高.     

CRYSTAL STRUCTURE OF Mo_3(μ_3-O) (μ-S_2)_ 3 [S_2P(OEt)_2]_3I

<正> Mr=1178.9, monoclinic, P21/n, a=16.570(2), b=12.370(1), c=20.007(2) A,β=99.97(1)°, V=4039.0A3, Z=4, Dx=1.938 Mgm-3, λ(MoKα)=0.7107A, μ(MoKα)=23.96 F(000)=2296, room temperature. Final R value=0.047 for 4387 unique observed reflections. It consists of neutral mono-oxo-capped trinuclear molybdenum cluster molecules with an average Mo-Mo bond length of 2.626(4)A and an average Mo-0 bond length of 2.036(2)8.