[C5H4C(CH3)(C3H7)CH2CH=CH2]NdMg2(μ3-OH)(μ3-Cl)(μ2-Cl)3(THF)4Cl的合成和晶体结构分析

用Ｘ－射线衍射法测定了［Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ３Ｈ７）ＣＨ２ＣＨ＝ ＣＨ２］ＮｄＭｇ２（μ３－ＯＨ）（μ３－Ｃｌ）（μ２－Ｃｌ）３（ＴＨＦ）４Ｃｌ的晶体结构。它属三斜晶系,空间群为Ｐ１－ ,ａ＝ １２．６９８（３）, ｂ＝ １３．６１６（３）, ｃ＝ １３．７１２（３）, α＝ ６８．９１（３）, β＝ ８４．３４（３）, γ＝ ６３．０７（３）°, Ｖ＝ １９６６（１）３, Ｍｒ＝ ８４９．７４, Ｄｘ＝ １．４１２ ｇ·ｃｍ － ３, μ＝ １．７２９７ ｍ ｍ － １, Ｆ（０００）＝ ８４０, Ｚ＝ ２, Ｒ＝ ０．０７３, ｗ Ｒ＝ ０．０８６（Ｉ≥３σ（Ｉ））。分子中Ｎｄ（Ⅲ）原子的配位数为八,形成一个严重扭曲的八面体结构。两个Ｍｇ 原子的配位情况相似,它们的配位数都是六,构成两个扭曲的八面体。这三个八面体通过三个共用平面联接     

Study of allylic rearrangement in (μ-H)Os3(μ-O=CNRCH2CH=CH2)(CO)10 (R=H or CH3) clusters

The migration of the double bond in the allylcarboxamide ligands of (μ-H)Os₃(μ-O=CN RCH₂CH=CH₂) (CO)₁₀ (R=H (1) or CH₃ (2)), (μ-D)Os₃(μ-O=CNDCH₂CH=CH₂) (CO)₁₀, and (μ-H)Os₃(μ-O=CNHCD₂CH=CH₂)(CO)₁₀ clusters was studied by¹H,²H, and¹³C NMR spectroscopy. Neither μ-D nor ND groups in the deuterated complexes are directly involved in prototropic processes of allylic rearrangement. Initially, the deuterium atom of the CD₂ group migrates to the ψ-carbon atom of the allyl fragment to form the −CD=CH-CH₂D propenyl moiety, in which the deuterium and hydrogen atoms are gradually redistributed between the ψ-and β-carbon atoms. The triosmium cluster complexes containing the bridging carboxamide ligands O=CNRR' catalyze the allylic rearrangement ofN-allylacetamide. Based on the data obtained, the probable scheme of the allylic rearrangements in clusters1 and2 was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2182–2186, November, 1999.     

Synthesis, Structure and Properties of a Copper Complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2

The title complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2 1(C20H24Cu2O10, Mr=structure was determined by X-ray diffraction method. Complex 1 belongs to orthorhombic, space group Pbca with a = 13.083(6), b = 8.078(4), c = 21.566(2)(A), V = 2279(2) (A)3, Z = 4, Dc= 1.607g/cm3, F(000) = 1128,μ(MoKa) = 1.918 mm-1, the final R = 0.0506 and wR = 0.1382. Each Cu(Ⅱ)ion is coordinated by five oxygen atoms from two benzoic acids, two acetic acids and one methanol molecule in a slightly distorted square pyramidal environment. The title molecules construct a 2-D complex 1 displays strong emissions. IR and TG-DTA studies are also presented.     

The reaction of Sn[CH(SiMe3)2]2 with ethyne: formation of (HCC)Sn[CH(SiMe3)2]2(μ-trans-CHCH)Sn[CH-(SiMe3)2]2(CHCH2)

The reaction of Sn[CH(SiMe₃)₂]₂ and ethyne at ambient temperature affords a mixture of products, from which the title compound has been separated and identified by IR, ¹H, and ¹³C NMR spectroscopy.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-PhS) (μ-σ,π-CH_3CH = CH)Fe_2(CO)_6

<正> The crystal and molecular structure of (μ-PhS) (μ-σ, n-CH3CH = CH)-Fe2(CO)6 has been determined by X - ray diffraction technique. The complex has chemical formula of C15H10O6SFe2 and Mr=129. 99. The crystals are monoclinic,space group P21/c,with α=11. 789(2),b= 7. 159(1),c = 20. 890(4) A ;β = 100. 89(2);V = 1731. 32 A3;Z=4,Dc=1. 65g·cm-3;F(000) = 863. 86. The final R and Rw equal 0. 0315 and 0. 0405 respectively for 2527 observed unique reflections.     

Os3(CO)9(μ3-AsC6H4CH3)(μ3-C6H3CH3) synthesis and crystal structure

One of the products of the reaction of the activated cluster Os₃(CO)₁₁(NCMe) with As(p-tol)₃ in refluxing nonane has been shown by spectroscopic and X-ray crystallographic methods to be Os₃(CO)₉(μ₃-AsC₆H₄CH₃)(μ₃-C₆H₃CH₃), which contains a benzyne moiety bonded asymmetrically from one carbon to one osmium via a σ bond and from a second carbon to form a bridge between the remaining two osmium atoms.     

Complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2]: Synthesis,Structure, and Mass Spectrometric Studies

Russian Journal of Coordination Chemistry - Three new binuclear aqua-bridged nickel(II) 2-methylpropionate complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2] (L is...     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-SPh) (μ-SCH2CH2CN)Fe_2 (CO)_6

<正> The crystal and molecular structure of (μ-SPh)(μ-SCH2CH2CN)Fe2-(CO)5 has been determined by X-ray diffraction method. The crystals of this complex are triclinic, space group P1,with a=ll.175(1), b=ll.877(2), c= 15.640(2)1,α=106.20(1),β=103.15(1),γ=98.46(1)°; Z=4; Dc=1.67g/cm3. The final structure refinement converged with unweighted and weighted R factors of 0.028 and 0.034 for 2853 observed unique reflections.     

Intramolecular Rearrangements of >Si(O–C·=O)(CH2–CH3) and >Si(CH2–CH·–CH3)(CH2–CH3) Radicals

Using ESR and IR spectroscopy, the structures of >Si(O–C^·=O)(CH₂–CH₃) (1) and >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) (2) radicals were deciphered. The directions and kinetic parameters of reactions of intramolecular rearrangements in these radicals were determined. The reactions of hydrogen atom abstraction in radical (1) from the CH₂ and CH₃ groups were studied. It was found that the endothermic reaction of hydrogen atom abstraction from the methyl group occurs at a higher rate than the exothermic reaction with the methylene group. The differences are determined by changes in the size of a cyclic transition state. Based on the experimental data, the strengths of separate C–H bonds in surface fragments are compared. The rearrangement >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) >Si(C^·(CH₃)₂)(CH₂–CH₃) was discovered and its mechanism was determined. One of its steps is the skeletal isomerization Si- (2)- _. (1)Si- (1)- _. (2). Experimental data are analyzed using the results of quantum-chemical calculations of model systems.     

Syntheses and characterization of the vanadium trimer (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(4,4′-bipyridine) and the vanadium hexamer [(V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6]2(μ2-N1,N2-di(pyridin-4-yl)oxalamide)

Reacting VO(acac)₂ with six equivalents of dibenzylphosphinic acid in the presence of 4,4′-bipyridine or μ₂-N¹,N²-di(pyridin-4-yl)oxalamide leads to trimeric (V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆(4,4′-bipyridine) or the hexamer [(V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆]₂(μ₂-N¹,N²-di(pyridin-4-yl)oxalamide). The complexes were characterized by spectroscopic (FTIR and ¹H NMR spectroscopies), TGA, and by single crystal X-ray diffraction measurements. The structures consist of a planar central core where three vanadium ions are arranged in the form of a quasi-isosceles triangle and contain an interstitial O which is multiply bonded to one V and weakly interacting at different bond distances to the remaining two V ions.     

The synthesis and crystal structure of novel Mo-Sn tetranuclear cubane-like cluster [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2)

The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo₃(SnBr₃)(μ ₃-O)(μ ₃-S)₃(dtp)₃(py)₃]·(CH₂Cl₂) (A) (dtp=S₂P(OC₂H₅)₂) are reported. The compound is prepared by the reaction of [Mo₃(μ ₃-O)(μ-S)₃(dtp)₄·(H₂O)] with SnBr ₃ ^? . The molecular structure of the cluster can be described as a [Mo₃OS₃] core with the SnBr ₃ ^? fragment linked to {Mo₃} triangle by three (μ ₃-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C_3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr ₃ ^? may cause electron transfer from Sn²⁺ to [Mo₃OS₃] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P2₁/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)ų, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,R _w=0.064.     

反常蓝移单电子锂键Y…Li-CH3[Y=CH3, CH2CH3, CH(CH3)2, C(CH3)3]体系的结构与性质

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   

Synthesis and characterisation of novel selenium-containing clusters; crystal structures of [Ru4(μ4-Se)2(CO)8(μ-CO)3] and [Ru3(μ3-Se)2(CO)7(Ph2P(CH2)3PPh2)]

The compound [Ru₄(μ-Se)₂(CO)₈(μ3-CO)₃] (1), has been obtained in good yield by vacuum pyrolysis of [RU₃(CO)₁₂] with [Ph₂Se₂] at 185°C. Reaction of 1 with 1,3-bis(diphenylphosphino)propane at room temperature affords the novel cluster [RU₃(μ₃-Se)₂(CO)₇(Ph₂P(CH₂)₃PPh₂)] (2). The structures of 1 and 2 have been determined by an X-ray diffraction study.     

簇合物C03(CO)7(μ3-S) [μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH]和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)]的合成与晶体结构

用Co2(CO)8分别与两个杂环配体C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反应.合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1空间群,I的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有C0作为端基配体与三个Co原子成键.I中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件.     

Preparation and reactivity of metal-containing monomers 53. Synthesis and stability of a cluster monomer (μ-H)Os3(μ-OCNMe2)(CO)9PPh2CH2CH=CH2 in solution

The stability of the complex (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₂CH₂CH=CH₂ (1), which contains a free unsaturated functional group in the terminal ligand PPh₂CH₂CH=CH₂, with respect to isomerization, chelation of the ligand, and other transformations in solutions was examined. No transformations of complex1 were observed in the course of synthesis from (μ-H)Os₃(μ-OCNMe₂)(CO)₉NMe₃ or upon heating in solution. Complex1 as well as complexes (μ-H)Os₃(μ-OCNMe₂)(CO)₉PHPh₂ and (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₃, which were formed as admixtures, were isolated in the solid state and identified by¹H,¹H-{³¹P}, and¹H-{¹H} NMR, IR, and Raman spectroscopy and mass spectrometry. For Part 52, see Ref. 1. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1455–1460, August, 2000.     

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.     

(CH2)2N和(CH3)2NH+的密度泛函理论计算

用密度泛函理论UB3LYP／6-31G（d,p）方法研究了二甲胺自由基（CH3）2N及其质子化离子（CH3）2NH 的构象和超精细结构．在由构象研究得到的两种自由基的最稳定结构上,用密度泛函的UB3LYP和UB3PW91方法及从头计算的UHF、UMP2（FULL）方法计算了α-质子、β-质子和N核上的超精细偶合常数A（Hα）、A（Hβ）和A（N）结果表明：两种自由基中甲基内旋转的位垒均很低,分别为0．46kJ·mol-1（（CH3）2NH ）和2．6kJ·mol-1（（CH3）2N）．UB3LYP／6-31G（d,p）和UB3PW91／6-31G（d,p）计算的A（Hα）、A（Hβ）和A（N）与ESR实验结果符合得很好,UMP2／6-31G（d,p）方法的计算值与实验值符合得也较好．     

Cluster Complexes of Polythioether Macrocycles: The Synthesis and Molecular Structures of Ru6(CO)13(cis-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C) and Ru6(CO)13(trans-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C)

The reaction of a mixture of cis-3,7,11-trimethyl-1,5,9-trithiacyclododecane, cis-Me₃12S3, 1 and trans-3,7,11-trimethyl-l,5,9-trithiacyclododecane, trans-Me₃12S3, 2, with Ru₆(CO)₁₇(μ ₆-C), 3, yielded three new cluster compounds Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 4, and two isomers of Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 5a and 5b. The molecular structures of 4 and 5b were established by single crystal X-ray diffraction analyses. In both complexes, the macrocycles have adopted tridentate coordination with one of the sulfur atoms in a bridging position. Two carbonyl ligands occupy bridging positions in each compound. Crystal Data for 4·Me₂CO: space group=P2₁/n, a=11.295(1) Å, b=17.547(3) Å, c=20.318(3) Å, β=93.71(1)°, Z=4, 2900 reflections, R=0.025. Crystal Data for 5b·1.5 C₆H₆: space group=Pbca, a=31.8900(8) Å, b=23.4330(6) Å, c=21.6240(4) Å, Z=16, 12163 reflections, R=0.040.