Synthesis and crystal structure of [W3S4(Acac)3(PPh3)3]PF6 · 0.5CHCl3 and [W3S4(Hfac)3(PPh3)2Br] · 2CHCl3

New cluster complexes [W₃S₄(Acac)₃(PPh₃)₃]PF₆ · 0.5CHCl₃ (Acac = CH₃C(O)CHC(O)CH₃) (I) and [W₃S₄(Hfac)₃(PPh₃)₂Br] · 2CHCl₃ (Hfac = CF₃C(O)CHC(O)CF₃) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. The cis-cis type of coordination of acetylacetonate and hexafluoroacetylacetonate ligands in I and II, respectively, was established, and the PPh₃ ligands were found in the trans-positions with respect to the “capping” sulfide ligand (μ³-S).     

Crystal structure of K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O

By the reaction of [Mo₃S₄(C₂O₄)₃(H₂O)₃]²⁻ with PdCl₂ and NH₄H₂PO₂ as a reducing agent, followed by the addition of PPh₃, a new oxalate cuboidal cluster complex [Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]²⁻ is obtained. It was isolated and structurally characterized as K₂[Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]·0.5H₂O. Original Russian Text Copyright ? 2008 by A. L. Gushchin, M. N. Sokolov, D. Yu. Naumov, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 775–778, May–June, 2008.     

Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

The reduction of trans-[Pd(NHC)₂Cl₂] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IⁱPr₂ = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd₃(μ-CO)₃(NHC)₃] (NHC = IMes, 1; IⁱPr₂, 3). Treatment of 1 with SO₂ at room temperature yields the bridging SO₂ complex [Pd₃(μ-SO₂)₃(IMes)₃] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography.     

Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

A reaction of the dimer [Mn(CO)₄(SPh)]₂ with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic complex (CO)₄Mn(μ-SPh)Pt(PPh₃)₂ (I) and its isomer (CO)₃(PPh₃)Mn(μ-SPh)Pt(PPh₃)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)₃Mn(μ-SPh)Pt(PPh₃)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P, 2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Novel chromium trinuclear trifluoroacetate complexes Cr3(μ3-O)(CF3COO)6(CH3COOH)2(CF3COO) and Cr3(μ3-O)(CF3COO)6(CH3COOH)2(THF): Synthesis and crystal structure

Novel anhydrous trinuclear ₃-oxo complexes of Cr(III), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(CF₃COO) (I) and of Cr(III,III,II), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(THF) (II) (where THF is (CH₂)₄O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna2₁, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R ₁ = 0.0332; complex II crystallizes in monoclinic system: space group P2₁/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(₃-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.     

Crystal structure of [Rh(Thio)6](NO3)3·3H2O and [Pd(Thio)4](NO3)2 thiourea complexes — products of extraction tretament of rhodium(III) and palladium(II) nitrate-nitrite solutions

The products of the extraction treatment of Rh(III) and Pd(II) nitrate-nitrite solutions are studied. The [Rh(Thio)₆](NO₃)₃·3H₂O and [Pd(Thio)₄](NO₃)₂ complex salts are extracted and an X-ray diffraction analysis of single crystals is performed (BRUKER X8 APEX automated diffractometer, MoK _a radiation, graphite monochromator, two-dimensional CCD-detector). [Rh(Thio)₆](NO₃)₃·3H₂O crystallographic characteristics are as follows: _a = 15.1857(3) ?, _b = 10.7292(2) ?, _c = 18.8524(4) ?, β = 105.165(1)°, P2 ₁ /c space group, _Z =4; [Pd(Thio)₄](NO₃)₂: a = 5.8013(4) ?, b = 7.0981(5) ?, c = 11.4991(8) ?, α = 99.963(2)°, β = 101.410(2)°, γ = 102.229(2)°, P —1 space group, Z = 1.     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

Cr2(WO4)3和Cr2(MoO4)3的负热膨胀特性研究

用液相反应-前驱物烧结法制备了Cr₂(WO₄)₃和Cr₂(MoO₄)₃粉体。298～1 073 K的原位粉末X射线衍射数据表明Cr₂(WO₄)₃和Cr₂(MoO₄)₃的晶胞体积随温度的升高而增大, 本征线热膨胀系数分别为(1.274±0.003)×10^-6 K^-1和(1.612±0.003)×10^-6 K^-1。用热膨胀仪研究了Cr₂(WO₄)₃和Cr₂(MoO₄)₃在静态空气中298～1 073 K范围内热膨胀行为，即开始表现为正热膨胀，随后在相转变点达到最大值，最后表现为负热膨胀，其负热膨胀系数分别为(-7.033±0.014)×10^-6 K^-1和(-9.282±0.019)×10^-6 K^-1。     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Diverse coordination of two ligands in ferromagnetic [Cu(μ-HCO2)2(3-pyOH)]n and [Cu2(μ-HCO2)2(μ-3-pyOH)2(3-pyOH)2(HCO2)2]n

Two novel polynuclear complexes with methanoate anions and 3-hydroxypyridine ligands [Cu(μ-HCO₂)₂(3-pyOH)]_n (1) and [Cu₂(μ-HCO₂)₂(μ-3-pyOH)₂(3-pyOH)₂(HCO₂)₂]_n (2), respectively, were synthesized and characterized. The central copper atom in 1 is surrounded by four methanoates and a 3-pyOH molecule, forming a square-pyramidal CuO₃NO chromophore. All the methanoates are bidentate and serve as bridges between the adjacent copper ions via syn-anti and anti–anti coordination. The basal square coordination axes are formed by O(syn), N(3-pyOH) (1.974(2), 2.016(2) Å) and O(anti), O(anti) (1.945(2), 1.960(2) Å), while the third O(anti) (2.247(2) Å) is on the top of the pyramid. A ferromagnetic transition with an exchange constant 2J/k_B = 9.2 cm⁻¹ is found for 1 below 20 K. This interaction probably takes place through two syn-anti methanoates extended in a chain through the 2D structure. On the other hand, two monoatomic Cu–O–Cu intra-dinuclear asymmetric (1.986(2), 2.415(2) Å) bridges of two methanoates in [Cu₂(HCO₂)₄(3-pyOH)₄] (2) are present. An elongated distorted octahedral coordination sphere around each copper(II) atom is completed by an additional monodentate terminal methanoate (1.975(2) Å), two N-coordinated 3-pyOH (2.005(2), 2.002(2) Å) and the third weakly O-coordinated 3-pyOH (2.732(2) Å). Although a shorter Cu?Cu distance is noticed in 2 than in 1 (4.690(1) Å 1, 3.442(1) Å 2), much weaker ferromagnetism is found in 2.     

Ni-P-Zn3(PO4)2(ZnSnO3、ZnSiO3)纳米复合化学镀层性质和组成的研究

研究了温度、时间、浓度等对Ａ３钢片上Ｎi-P-Zn3(PO4)2、Ni-P-ZnSnO3和Ｎi-P-ZiSiO3纳米复合合化学镀层外貌的影响,用扫描电子显微镜（ＳＥＭ）观察外貌、称重法测定厚度;通过１０％ＮaCl溶液、１％Ｈ２Ｓ气体加速腐蚀试验,１０％ＣuSO4溶液点滴试验等多种手段测定其耐腐蚀性能,用Ｘ－射线光电子谱（ＸＰＳ）及俄歇电子能谱（ＳＥＳ）测定其价态组成,结果表明：在最佳施镀条件下,可得光亮、致密、耐腐蚀性强于Ａ３钢、磷化膜及Ｎi-P镀层的纳米复合化学镀层,镀层的原子百分组成约为（％）：Ｎi-P-Zn3(PO4)2:Ni70.00,P12.47,Zn3(PO4)213.93,C3.6;Ni-P-ZnSnO3;Ni77.56,P10.00,ZnSnO39.84,C2.6;Ni-P-NiSiO3,Ni83.00,P10.96,ZnSi5.15,C0.89.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Dynamic behavior of [(η-C5H4CH3)Cr(CO)2(μ-SBu)Pt(PPh3)2] in solution

The structure and dynamic behavior of complex [(η⁵-C₅H₄CH₃)Cr(CO)₂(μ-SBu)Pt(PPh₃)₂] in solution was studied by multinuclear (¹H, ¹³C, ³¹P) NMR spectroscopy including a phase-sensitive NOESY experiment. Increasing temperature causes rupture of the Cr-Pt bond in the three-membered ring of the complex and rotation of the S-Pt(PPh₃)₂ unit around the Cr-S bond line, followed by formation of a new Cr-Pt bond to close the ring. All activation parameters for this dynamic process have been determined.     

Reactions of Cu3(dppm)3(μ3-OH)(ClO4)2 (dppm = bis-(diphenylphosphino) methane) with Soft Heterocumulenes

The reaction of [Cu₃(dppm)₃(μ₃-OH)](ClO₄)₂ (1) with heterocumulenes (XCS; X = NPh, NMe and S) has been studied. The μ₃-OH ligand inserts into PhNCS and MeNCS only in the presence of methanol. Insertion products are formed in accord with earlier observations made with copper(I)-aryloxides. On heating, the insertion products convert to a S bridged cluster [Cu₄(dppm)₄(μ₄-S)](ClO₄)₂ (8), having a tetrameric core. However, in the reaction with CS₂, 1 is converted to 8 even at room temperature in the presence of methanol. On the other hand, the dimeric complex [Cu₂(dppm)₂(CH₃CN)₄](ClO₄)₂, reacts with CS₂ to give (diphenylphosphinomethyl)-diphenylphosphine sulfide, Ph₂P-CH₂-P(S)Ph₂ (dppmS), which forms the complex [Cu(dppmS)₂]ClO₄ (9). A single crystal X-ray crystallographic study of 9, the first copper(I) complex of dppmS has been taken up to confirm the mono-oxidation of the dppm ligand and the nuclearity of the complex. Reactions of complex 1 with heterocumulenes and with elemental sulfur, are compared.     

Synthesis,X-ray crystal structure and thermal decomposition of two peroxovanadium complexes with coordinated ammonia molecules: [{VO(O2)2(NH3)}2{μ-Cu(NH3)4}] and [Zn(NH3)4][VO(O2)2(NH3)]2

The compounds [{VO(O₂)₂(NH₃)}₂{μ-Cu(NH₃)₄}] (1) and [Zn(NH₃)₄][VO(O₂)₂(NH₃)]₂ (2) were prepared and characterized by elemental analysis and infrared spectra. The single crystal X-ray study revealed that the structure of 1 consists of trinuclear complex molecules [(NH₃)OV(O₂)₂{μ-Cu(NH₃)₄}(O₂)₂VO(NH₃)] with a rare heterobimetalic peroxo bridge: copper(II)–peroxo ligand–vanadium(V). The structure of 2 is composed of tetraamminezinc(II) cations and ammineoxodiperoxovanadate(V) anions. In course of thermal decomposition of 1 performed up to 620 °C, the following intermediate products: [Cu(NH₃)₂(VO₃)₂], and subsequently a mixture of V₂O₅ with monoclinic β-Cu₂V₂O₇, were gradually formed. The final product of decomposition is Cu(VO₃)₂. The thermal decomposition of 2 is a two-step process. In the first stage, [Zn(NH₃)₃(VO₃)₂] as supposed intermediate was formed, which transformed at higher temperatures by release of ammonia molecules to the monoclinic modification of Zn(VO₃)₂.     

The crystal structure of Yb2(SO4)3·3H2O and its decomposition product, β-Yb2(SO4)3

Yb₂(SO₄)₃·3H₂O, synthesised by hydrothermal methods at 220(2) °C, has been investigated by single crystal X-ray diffraction. Yb₂(SO₄)₃·3H₂O crystallises in space group Cmc2₁ and is isostructural with Lu₂(SO₄)₃·3H₂O. The crystal structure has been refined to R₁=0.0145 for 3412 reflections [F_o>3σ(F)], and 0.0150 for all 3472 reflections. The structure of Yb₂(SO₄)₃·3H₂O is a complex framework of YbO₆ octahedra, YbO₈ and YbO₅(H₂O)₃ polyhedra and SO₄ tetrahedra. Thermal data shows that Yb₂(SO₄)₃·3H₂O decomposes between 120 and 190 °C to form β-Yb₂(SO₄)₃. The structure of a twinned crystal of β-Yb₂(SO₄)₃ was solved and refined using an amplimode refinement in R3c with an R₁=0.0755 for 8944 reflections [F_o>3σ(F)], and 0.1483 for all 16,361 reflections. β-Yb₂(SO₄)₃ has a unique structural topology based on a 3D network of pinwheels.     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.