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1.
The disproportionation reaction of the subvalent metastable halide SnBr proved to be a powerful synthetic method for the synthesis of metalloid cluster compounds of tin. Hence, the neutral metalloid cluster compound Sn(10)[Si(SiMe(3))(3)](6) (3) was synthesized from the reaction of SnBr with LiSi(SiMe(3))(3). In the course of the reaction anionic clusters might also be present, and we now present the first anionic cluster compound {Sn(8)E[Si(SiMe(3))(3)](3)}(-) (E = Si, Sn), where one position in the cluster core is occupied by a silicon or a tin atom, giving further insight into structural variations of E(9) cages in metalloid group 14 cluster compounds.  相似文献   

2.
The hydrothermal reaction of MoO3, V, Na2WO4· 2H2O, [N(CH2CH2)3N](1,4-diazabicyclo[2.2.2] octane), and H2O at 160°C for 90h gave dark-brown crystals of [HN(CH2CH2)3N]2[HMoVMoVI 5O19]·[N(CH2CH2)3N], (1), in 40% yield. Complex (1) is the first one-electron reduced mixed-valence hexamolybdate to be crystallized and structurally characterized. The crystal structure of (1) consists of discrete [HMoVMoVI 5O19]2– anions, [HN-(CH2CH2)3N]+ cations, and neutral [N(CH2CH2)3N] molecules of crystallization.  相似文献   

3.
《Polyhedron》1999,18(26):3533-3544
[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]2−, [Q]2[Sn(C3S5)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(C3S4O)3], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]2− [Q]2[Sn(C3S3Se2)3], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]2[Sn(C3S5)3] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe4, NEt4, and PPh4) and [NEt4]2[Sn(C3S4O)3] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe4, in chains for the somewhat larger cation, NEt4 and is absent for the still larger, PPh4 cation.  相似文献   

4.
5.
Reaction of the disilyne-NHC complex 1 [RLSi═SiR: (R = Si(i)Pr[CH(SiMe(3))(2)](2), L = NHC)] with MeOTf gave the cation 2 [RLSi═SiRMe](+), which is the first example of a base-stabilized heavy group 14 element analogue with vinyl cation character. Cation 2 has been fully characterized by multinuclear NMR spectroscopy and X-ray diffraction analysis. The molecular structure indicates that there are significant contributions from the NHC-stabilized cationic resonance structure 2A, the disilene-like structure 2B, and even some contribution from the silylene-like structure 2C.  相似文献   

6.
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.  相似文献   

7.
Tris(substituted butadiene) complexes of molybdenum and tungsten have been prepared by the reduction of the metal halides with anthracene-activated magnesium in the presence of the appropriate diene. An X-ray diffraction study has shown tris(2,3-dimethylbutadiene)molybdenum and its tungsten analogue to be isomorphous, with each diene unit displaying a long—short—long bond alternation, and having short metal to terminal carbon atom distances, in marked contrast to the unsubstituted complexes.  相似文献   

8.
The reaction of bis(dibromophenylstannyl)methane with 1, 3-bis(3, 5-dimethyl- pyrazol-1-yl)propane in a 1:1 or 1:2 ratio yields only 1:1 adduct which partly hydrolyzes to the title complex (C26H38Br6N4O2Sn2, Mr = 1155.42) during crystal growing. The title complex is of triclinic, space group P ī with a = 10.886(1), b = 12.508(1), c = 13.879(1) ?, α = 85.762(2), β = 85.159(2), γ = 84.020(2)°, V = 1868.8(4) ?3, Z = 2, Dc = 2.046 g/cm3, λ(MoKα) = 0.71073 ?, μ = 7.778 mm-1, F(000) = 1088, R = 0.0488 and wR = 0.1157 for 7560 observed reflections with I ≥ 2σ(I). The crystal structure analysis indicates that there is no direct interaction between the ligand and bis(dibromophenylstannyl)methane, and two tin atoms are bridged by two bromide atoms from the partial hydrolysis of this adduct.  相似文献   

9.
10.
The Platinum(II) diamine with N,N-dimethylethylenediamine (N,N-dimeEn) [Pt{(CH3)2N(CH2)2NH2}Cl2] (I) was synthesized. The reaction of the diamine with pyridine gave Pt(II) tetramine [Pt{(CH3)2N(CH2)2NH2}Py2]Cl2 (II), which was oxidized with chlorine to give Pt(IV) triamine Pt{[(CH3)2N(CH2)2}PyCl3]Cl · H2O (III). The reaction of III with chlorine (chloroamidation) yielded chloroimide [Pt{(CH3)2N(CH2)2NCl}PyCl3] (IV). The IR spectra of complexes I–IV and UV/Vis spectra of III and IV were studied. X-Ray diffraction analysis was performed for III (monoclinic crystals, space group P21/c, a = 7.7437(6), b = 8.1100(7), c = 28.52992(2) Å, β = 93.7280(10)°, Z = 4, R hkl = 0.0420) and IV (orthorhombic crystals, space group Pna21, a = 15.7825(12), b = 7.4447(6), c = 12.3099(6) Å, Z = 4, R hkl = 0.0539). During oxidation of Pt(II) tetramine with chlorine, the pyridine molecule is removed from the cis position relative to the (CH3)2N group (trans position relative to the NH2 group) of N,N-dimethylethylenediamine. The reaction of chloroimide complex IV with concentrated HCl (dechloroamidation) at 20°C afforded the initial complex III; that at 100°C, gave triamine III together with Pt(IV) diamine [Pt(N,N-dimeEn)Cl4] (V) (monoclinic crystals, space group P21/n, a = 7.1278(5), b = 11.5384(8), c = 12.7501(9) Å, β = 93.23(10)°, Z = 4, R hkl = 0.0239).  相似文献   

11.
吴鼎铭  黄小荥 《结构化学》1994,13(5):385-388
SynthesisandStructureof[HOCH_2CH_2N(CH_3)_3]_4[Cu_4OCl_(10)]WuDing-Ming;HuangXiao-Ying;ZhuangHong-Hui(StateKeyLaboratoryofStruct?..  相似文献   

12.
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 = O2?, 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.  相似文献   

13.
The complex [Pt2(μ-pp3)2] (pp3 = P(CH2CH2PPh2)3), produced by treatment of [PtH(pp3)]+ with sodium amalgam, has been shown to react with methyl iodide to give [PtMe(pp3)]+. The new complexes have been characterized by 1H, 31P and 195Pt NMR spectroscopy.  相似文献   

14.
The reactions of mononuclear carbene complexes of W and Fe of the type CO)mMC(OR)(CH2nCHCR′″ (M  = FE, W; m = 4 and 5; n = 0, 2, 3; R′, R″ = C, CH3, OEt) with Fe(CO)5 have been studied. In all cases the reaction leads to new hetero (WFe) or homo (FeFe) μ-alkylidene complexes, the position of the double bond depending strongly on n.  相似文献   

15.
Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl2] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py2]Cl2 (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl3]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH2 group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH3)2N(CH2)2C(O)NH”(Py)Cl3] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R hkl = 0.036. The crystals of V are monoclinic, space group P21/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R hkl = 0.052.  相似文献   

16.
在密度泛函理论B3LYP/6-311++G(d,p)及MP2/6-311++G(d,p)水平上研究了单电子锂键复合物Y…Li—CH3[Y=CH3, CH2CH3, CH(CH3)2, C(CH3)3]的结构与性质. 结果表明, 三种单电子锂键复合物H3CH2C…Li—CH3(II), (H3C)2HC…Li—CH3(III)和(H3C)3C…Li—CH3(IV)单电子锂键强度依II(-26.7 kJ·mol-1)相似文献   

17.
Proton spin—lattice relaxation time (T1) is measured in [N(CH3)4]PbX3 (XCl, Br, I) from 300-77 K at 9.75 MHz. All the compounds show discontinuous changes in T1 values (at 256, 270 and 277 K, respectively), indicating phase transitions. Single T1 minimum is observed in all the cases and the T1 variation is explained in terms of [N(CH3)4] and CH3 group dynamics. The activation energy Eα decreases from chloride to iodide (from 4 to 2 kcal/mol). In bromide and iodide, T1 is found to decrease with increase in temperature at higher temperatures, indicating the presence of spin—rotation interaction.  相似文献   

18.

Reaction of (Me 2 SnBr) 2 w -(CH 2 ) 3 with 2,2'-bipyridine (bpy) in benzene affords, in the presence of small amounts of water, crystals of the novel composite [Sn 2 (H 2 O) 2 Br 2 Me 4 { w -(CH 2 ) 3 }2bpy] ( 1 ). The crystal structure of 1 consists of alternating layers of either organotin bromide or bipyridine molecules, each bpy molecule being configured cis oid and linked with the organotin layer via one O-H > N hydrogen bond. The mutual disposal of the molecules in the bpy bilayer differs from that known for pure, crystalline bpy. Cell parameters: a 24.3499(1), b 6.5112(1), c 23.3262(1) Å; g 119.557(1). Monoclinic, space group C 2/ c , D calc =1.750 g/cm 3 , Z =4; final R 1: 0.0529; wR 2=0.1374 for 3638 unique reflections [ R (int)=0.0676; I >2 ( I )].  相似文献   

19.
After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH2(CH2)4NH2, we report chemical preparation and crystal structure for a new example of such compounds. [NH3(CH2)4NH3]2P4O12.2H2O is monoclinic (S.G. : P21/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P4O12 rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.  相似文献   

20.
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