Bis（C—p—carboranyl）（C2B10H11）2振动光谱的从头算研究

BiS（C-p-carboranyl）（C2B10H11）2是一种稠合型碳硼烷，由2个C2B10H11集团通过C-C键联结构成．Leites已发表了其实验振动光谱[1]，理论计算尚未见报道，本文对其几何优化、振动光谱及其指认进行从头计算研究．1计算方法首先在STO－3G下对标题化合物D5d与D5h两种构型进行从头算，确定D5d为其稳定构型，进而保持D5d对称性不变，并在6－31G下进行几何优化及振动光谱的理论研究，全部计算采用Gaussion－94程序，在CrayS－MP／11型计算机上完成．2结果与讨论2．1几何优化优化几何及部分实验键长列于表1．标题化合物在D5d与D5h两种…     

硼氢二茂铁铵盐的结构化学研究——Ⅲ.十二硼十二氢双(二茂铁甲基二甲基)铵晶体结构

标题的化合物晶体属斜方晶系,空间群为Pcnb,晶胞参数为:a=12.975(26),b=16.342(28),c=17.582(48),Z=4。晶体结构用直接法,三维Patterson函数和差值Fourier方法解出,经全矩阵最小二乘法修正,对1674个独立衍射点[I≥3σ(I)],最后偏离因子R=0.054。 该化合物属于离子型,阴离子和阳离子分别以六面体和四面体配位。     

Synthesis and Crystal Structure of Nido 11-Vertex Platinaborane [ （PPh3）2PtB10H10-9,10-（H0.7Cl0.3）2]

The reaction of PtCl2（PPh3）2 with closo-[B10H10]^2- in t-BuOH under reflux （70 h） unexpectedly afforded the nido 11-vertex platinaborane [（PPh3）2PtB 10H10-9,10-（H0.7Cl0.3）2] 1, which was characterized by single-crystal X-ray diffraction study. Crystallographic data for 1： C36H41.40B10Cl0.60P2Pt, Mr = 860.49, triclinic system, space group P1, a = 11.255（2）, b = 11.623（2）, c = 17.148（3）A, α = 81.012（2）, β = 88.115（3）, γ=64.322（2）°, V= 1995.4（7）A^3, Z= 2, Dc = 1.432 g/cm^3, μ（MoKα） = 3.662 mm^-1, F（000） = 851, R = 0.0358 and wR = 0.0951. Compound 1 has a nido 11-vertex {PtB10} polyhedral skeleton with the Pt atom lying in the open PtB4 face and further ligating to two PPh3 ligands. 1 is partially chlorinated at positions B（9） and B（10）, and for each chlorine atom an occupancy factor of 0.3 is given by crystallography.     

Localized molecular orbital studies on B_4C1_4,1,5-C_2B_3H_5 and B_nH_n~(2-)(n = 6-10, 12)

The wave functions, level energies and Mulliken population analysis of localized molecular orbitals (LMO's) for B4Cl4, 1,5-C2B3H5 and the closo-BnHn2- (n = 6-10, 12) are calculated by using the Edmiston-Reudenberg energy localization scheme under the CNDO/2 approximation in order to reveal the nature of quasi-aromaticity of the closo-BnHn2- (n > 5). It has been found that all the B-H or B-Cl LMO's are highly localized between the B and H (or Cl) atoms, corresponding to B-H or B-Cl o-bond, while the Bn framework bonding is formed mainly by the three-centered two-electron B-B-B bonds on the polyhedral faces. In the cases of B4Cl4 and 1,5-C2B3H5, these three-centered B-B-B bonds just fill their polyhedral faces; however, for the framework bonding of the closo-BnHn2- (n > 5), the valence electron deficiency leads to the delocalization of their three-centered B-B-B bonds, and as delocalizability of this three-centered B-B-B bond increases, some three-centered B-B-B bonds are further delocalized to become a f     

[Nd_2O(C_5H_5)_6](C_12H_9N_2)3Cl·mC_4H_8O的晶体结构

本文报告用单晶X-射线衍射法测定[Nd_2O(C-5H_5)_6](C_(12)H_9N_2)_3C1·mC_4H_5O的晶体结构。晶体属于单斜晶系,空间群为P2-1/c,晶胞参数为a=20.982(15),b=11.217(7),c=32.954(32),β=104.17(7)°;Z=4。Nd和C1原子坐标用直接法定出,其他原子坐标以差Fourier方法求得,经过最小二乘法修正,R因子为0.159。在分子中三个茂环皆通过η~5。键与Nd原子配位,两个Nd原子间存在桥氧原子,因而形成(Nd_2O(C_5H_5)_6)~(2-)阴离子,Nd-C键基本上属于离子键。三个邻菲罗啉基团通过氢键与C1原子连接形成大的阳离子[(C_(12)H_9N_2)3-C1]~(2+)。     

CRYSTAL STRUCTURE OF [Ni((C)_6H_(11)O)_2PS_2)·(C_4H_9NH_2)_4]-(C_6H_(11)O)_2PS_2

<正> [Ni((C6H11O)2PS2)·(C4H9NH2)4](C6H11O)2PS2,Mr-=938. 05, triclinic,P1,a=13. 513(6),b=16. 040 (7), c= 12. 891(6) A , α= 95. 66 (4),β= 90. 23(4),γ= 75. 46(3)°,V = 2691 A3,Z=2,Dc= 1. 16 g·cm3.μ=6. 07cm-1,MoKa radiation, λ=0. 71069 A ,F(000) = 1020,R=0. 100 for 4595 reflections with I≥3σ(I). The title compound molecule consists of a complex cation [Ni((C6H11O)2PS2)(C4H9-NH2)4]+ and a complex anion (C6H11O)2PS2- . The Ni (Ⅱ) atom in the cation is octahedrally coordinated by four nitrogen atoms from four w-butylamine ligands and two sulfur atoms from one (C6H11O)2PS2 group.     

硼氢二茂铁季铵盐的结构化学研究——Ⅰ、十硼十氢双(二茂铁甲基三甲基)铵晶体结构

本文报告了(C_5H_5FeC_5H_4CH_2N(CH_3)_3)_2B_(10)H_(10)晶体的结构。该晶体属三斜晶系、空间群为P_1~-。晶胞参数为:a=10.043(2),b=10.513(7),C=15.094(10),a=85.01(6),β=97.58(3),Υ=94.87(3)°,V=1625.7~3,Z=2。晶体在室温下用CAD-4四圆衍射仪收集衍射强度数据(MoKa),用重原子法解出铁原子坐标,综合应用E图、Fourief合成和差Fourier合成解出其他非氢原子坐标,按SDP加氢程序等求解阳离子中40个氢原子位置。各原子坐标及热振动参数经全矩阵最小二乘方修正,对于2258个独立衍射点(I≥3σI)],偏离因子R=0.043。 结构分析表明,B_(10)H_(10)~(2+)阴离子和C_5H_5FeC_5H_4CH_2N(CH_3)_3~+阳离子分别按畸变的八面体和畸变的三角形配位。两个二茂铁季铵阳离子中,两对戊二稀环平面间距为3.271(5)。阳离子中主要键长平均值为:Fe-C=2.026,C—C(环)=1.401,C—N=1.503。B_(10)H_(10)~(2+)阴离子为四方(三角)十六面体笼状结构,主要键长平均值为:B—B(顶点到正方形平面原子)1.706A,B—B(其它原子间)=1.830。     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C_(14)H_9O_4)(C_(14)H_(10)O_4)(C_(12)H_(12)N_2)_2] and [Ag(C_(14)H_9O_4)(C_(13)H_(14)N_2)]·0.5H_2O

1 INTRODUCTION Supramolecular approaches to self-assembly of infinite molecular solids with novel structural topo- logies attract considerable attention for their po- tential applications as functional materials and their fascinating architectures[1]. In…     

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [Cu_2(CH_3COO)_4(C_8H_(11)NO)_2] · (C_6H_(11)NO)_2 · (C_8H_(12))

<正> SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [Cu_2(CH_3COO)_4(C_8H_(11)NO)_2] · (C_6H_(11)NO)_2 · (C_8H_(12)), where C6H11 = caprolactam, Mr = 900. 07, triclinic,space group P1, a = 11. 103(4), b= 11. 865(6), c=9. 912(3)(?), α=94. 85(4), β=115.20(2), γ=103. 25(4)°, V = 1125(2)(?)3, Z = l, Dx = 1. 33g. cm-3, λ(MoKa) = 0. 71069(?), T = 295K , μ = 10. 45cm-1, F(000) = 478, final R=0. 063 for 2098 observed reflections with I>3σ (I). The two Cu atoms in the molecule are held together by four carboxylate groups. Each Cu atom is bound in a square-pyramidal configuration to four carboxyl oxygen atoms and to the O atom of a caprolactam molecule.     

十二硼十二氢镍乙二胺晶体结构的研究

Ni(en)_3B_(12)H_(12)晶体属于三方晶系,空间群为R_3,晶胞参数为:a=b=12.890(2),c=23.955(20),α=B=90°,Υ=120°,Z=6。在室温下用CAD-4衍射仪收集单晶衍射强度数据(MOK_α);重原子法和差Fourier法解出全部非氢原子坐标,用加氢程序定出全部氢原子的坐标。各原子坐标及热振动参数经全矩阵最小二乘方修正,对于985个独立衍射点[I≥3σ(I)]最后偏离因子R=0.069。结构分析表明,该化合物属于离子型,Ni(en)_-~(2+)离子和B_(12)H_(12)~(-2)离子间相互以正三角双锥方式配位。Ni(en)~(2+)离子具有D_3对称性,Ni-N平均键长为2.138,B_(12)H_(120~(-2)离子呈正二十面体构型,B-B平均键长为1.786。     

Cr(CNR)_3Cl_3和Cr(CNR)_3Cl_2B(C_8H_5)_4·H_2O(R=CH_2C_8H_5)的合成和性质研究

长期以来人们对羰基配合物进行了较为充分的研究,但忽略了与之对应的异腈配合物领域。本文在四氢呋喃溶剂中制得两个过渡金属异腈配合物,初步研究了它们的性质,并讨论了它们的红外光谱和热重分析。 1 实验部分 1。1 试剂和仪器 CrCl_3(thf)_3按文献合成。CNCH_2C_6H_5和NaB(C_6H_5)_4购自Aldrich试剂     

C12簇及其碳管烷C12H12的理论研究

C60和C70等碳笼烯的发现及其在新物质、新材料等研究领域中的重要性，激励人们去探索合成更多新型多面体碳簇化合物与碳元素类似物[1，2]．最近，两类新型多面体碳管笼烯的设想提出来了[3，4]应用HMO和MNDO方法对其稳定性变化规律、结构和成键特征进行了讨论.关于多苯的vanderWaals簇实验上已有广泛的调查[5，6]，理论上对其二聚物（C6H6）。的不同几何构型与稳定性进行了深入的研究[7]．本文采用abinitio计算有效势（effectivecorePotential）方法，对C12碳管元素簇和C12H12，碳管烷的平衡结构、稳定性和价键特征进行了理论预测．1…     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

CRYSTAL STRUCTURE OF （C8H8）Sm（2,4—C7H11）（THF）

<正> The crystal structure of (C8H8)Sm(2,4-C7H11)(THF)(2,4-C7H11 = 2, 4-dimethylpentadienyl) , Mr=421. 8, has been determined which, belongs to monoclinic space group P21 with a = 8. 682(3), 6 = 10. 968(3), c=9. 744(3) (?) ,β= 104.24(2)°, V = 899. 3(4)(?)3, Z = 2, Dc=1. 66g/cm3, μc=33. 2cm-1, F(000) = 422 and final R = 0. 041 for 2021 observed reflections with I≥ 2σ(I). The 2,4-dimethylpentadienyl group is in "U " conformation. The carbon-carbon bond distances within the pentadienyl ligand fall essentially in two sets. The average distance of external C - C bonds is shorter than that of the internal bonds.     

Synthesis, Spectroscopic Properties and Crystal Structure of (C_4N_2H_(12))_2Zr(C_2O_4)_4·H_2O

1 INTRODUCTION The researches on transition metal coordination complexes have been rapidly expanded because of their fascinating structural diversity and potential applications[1～4]. As we know, zirconium oxalates can be used as precursors in the synth…     

Microwave spectra and structures of 1,2-(ortho)- and 1,7-(meta)-carborane, C2B10H12

The microwave spectra of 1,2- and 1,7-dicarba-closo-dodecaborane(12), C(2)B(10)H(12) (ortho- and meta-carborane), have been recorded for the first time at room temperature in the 32-88 and 24-80 GHz spectral ranges, respectively. The spectra of the parent species (1,2-C(2)(11)B(10)H(12) and 1,7-C(2)(11)B(10)H(12)) have been assigned, together with those of four monosubstituted ((10)B) 1,2-C(2)(10)B(11)B(9)H(12) and 1,7-C(2)(10)B(11)B(9)H(12) isotopologues. The microwave spectra confirm that the structures of each of these two molecules are slightly distorted icosahedrons of C(2v) symmetry. A previous determination of the gaseous structures of these two carboranes by the gas electron-diffraction method was based on several assumptions about the B-B bond length differences. All B-B bond lengths have now been redetermined using the substitution (r(s)) method, which is independent of such restraints. Although several of the r(s) and electron-diffraction bond lengths are in good agreement, there are also differences of up to 0.026 ?. Quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level of theory have also been performed.     

A further study on closo boron hydrides B_(16)H_(16)~(2-)(D_2) and B_(16)H_(16)(Td) using ab initio molecular orbital theory

Ab initio molecular orbital calculations of doubly negative charged B16H162-(D2) and neutral B16H16(Td) have been done at the HF/6-31G level.They are predicted to be chemically and kinetically stable by vibrational analyses on their respective energy hypersurface of the HF/6-31G level.The geometrical structure of the species B16H1622-(D2) was discussed.     

Synthesis and Crystal Structure of {(PPh_3)_2CIRuCIRu(PPh_3) B_(10)H_8[OCH(CH_3)_2)]_2}

1INTRODUCTIONAlthoughseveralhundredpolyhedralmetallaboraneshavebeencharacterized,theincidenceofruthenaboranesisparticularlysurprising.(hThefirstpolyhedralruthenaboraneisstructurallytypifiedbythecompound[(PPh,)2RuB,,HS(OEt),j,whichisobtainedin40%yieldsfromthereactionbetweentRuCI,(PPh,),jandcloso-tB,,H,,j'--inCHCI,/EtOH.tZiWithCH,COOH/THFt'iandC,H,COOH/CH,CI,">insteadofCHCI,/EtOH,twocompoundsF{(PPh,)2Ru}~(p-MeCO,)3--(pH)z-{RuB,,H,}jand[(PPh,)2(PhCOO)RuB,,HSCljhav…     

C_(60)环酮衍生物C_(66)H_8O与C_(67)H_(10)O顺反异构体的结构及光谱研究

用AM1，INDO/CI方法研究了C60与2-环己烯-1-酮和2-环庚烯-1-酮[2+2]环加成所得衍生物C_(66)H8O和C67H1O的结构。结果表明，两种衍生物的顺反异构体都只具有C1对称，C66H8O的顺式异构具有较低的能量和较小的偶极矩，C67H10的顺式并构体能量较低，但偶极矩较大，以优化构型为基础，计算加成产物的UV谱，对电子跃迁进行了理论指认，并分析了光谱移动的原因。     

Untethered 4,1,2-MC(2)B(10) supraicosahedral metallacarboranes, their C,C'-dimethyl 4,1,6-, 4,1,8- and 4,1,12-MC(2)B(10) analogues, and DFT study of the (4,)1,2- to (4,)1,6-isomerisations of C(2)B(11) carboranes and MC(2)B(10) metallacarboranes

Reduction of the tethered carborane 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) followed by metallation with {CpCo} or {(p-cymene)Ru} fragments affords both C,C'-dimethyl 4,1,2-MC(2)B(10) and 4,1,6-MC(2)B(10) species. DFT calculations indicate that the barriers to isomerisation of both 4-Cp-4,1,2-closo-CoC(2)B(10)H(12) and 4-(η-C(6)H(6))-4,1,2-closo-RuC(2)B(10)H(12) to their respective 4,1,6-isomers are too high for this to be the origin of the unexpected formation of 4,1,6-MC(2)B(10) products (in marked contrast to the related isomerisation of 1,2-closo-C(2)B(11)H(13) to 1,6-closo-C(2)B(11)H(13)), and, indeed, the 4,1,2-species are recovered unchanged from refluxing toluene. Equally, the DFT-calculated profile for the isomerisation of [7,8-nido-C(2)B(10)H(12)](2-) to [7,9-nido-C(2)B(10)H(12)](2-) suggests that the unexpected formation of 4,1,6-metallacarboranes is unlikely to result from isomerisation of a reduced (nido) carborane following desilylation. Instead, the source of the 4,1,6-MC(2)B(10) compounds is traced to desilylation of 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) by Li or Na prior to reduction. The supraicosahedral metallacarboranes 1,8-Me(2)-4-Cp-4,1,8-closo-CoC(2)B(10)H(10), 1,12-Me(2)-4-Cp-4,1,12-closo-CoC(2)B(10)H(10) and 1,12-Me(2)-4-(p-cymene)-4,1,12-closo-RuC(2)B(10)H(10) are also reported with all new species characterised both spectroscopically and crystallographically.