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.     

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 -     

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 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.     

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?..     

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.     

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 structures of [Pd(NH3)3(NO2)][Rh(NH3)2(NO2)4] and [PdEn2][Rh(NH3)(NO2)5]·0.75H2O

The structure of double complex salts [Pd(NH₃)₃(NO₂)][Rh(NH₃)₂(NO₂)₄] and [PdEn₂][Rh(NH₃)(NO₂)₅]·0.75H₂O is determined by single crystal X-ray diffraction. In the structures, the main structural moieties are identified.     

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.     

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.     

Ce(ph3PO)(DBM)2(NO3)2的合成与鉴定

β-二酮络合物已获得广泛而深入的研究,Ce(Ⅳ)的β-二酮类络合物的研究也有报导^[1-3].但是,关于Ce(Ⅳ)的β-二酮与其它混合配体络合物的研究至今未见报导.我们以(NH₄)₂Ce(NO₃)₆为起始物质,经由双-(三苯基氧化膦)硝酸铈(Ⅳ)中间络合物在混合溶剂中与DBM反应制得该化合物.通过紫外、红外光谱以及¹HNMR谱等研究,对该络合物的性质进行了讨论.     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.