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1.
Thecarbonylationoforganichalides,catalyzedbytransition-metalcomPlexes,isareactionofindustrialinterestleadingtoawiderange0fproductslilieesters,aldehydes,awhdesandacids.Formanyyears,catalyticactivationandfunctionalisationofthecarbonthalogenbondsinorganichalideshavebeenoneofthemostchallengingproblemsanddesirablegoalsforchendsts.Oforganichalides,0rgancchlorideisthemodrmaforeundiDexPdrieerefD1thepeDfu3efulboinboLalindusny.However,because0ftheinertness0ftheirC-Clbonds,organicchloridesexhibitl0wre… 相似文献
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Glöckner A Bannenberg T Büschel S Daniliuc CG Jones PG Tamm M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(22):6118-6128
The transmetalation reaction between [(η(7) -C(7) H(7) )ZrCl(tmeda)] (1; tmeda=N,N,N',N'-tetramethylethylenediamine) and various phospholide anions leads to a new class of mixed sandwich complexes: [(η(7)-C(7)H(7))Zr(η(5)-C(4)PMe(4))] (2), [(η(7)-C(7)H(7))Zr(η(5)-C(4)PH(2)Me(2))] (3) and [(η(7)-C(7)H(7))Zr(η(5)-C(4)PPhHMe(2))] (4). The presence of Lewis basic phosphorus atoms and Lewis acidic zirconium atoms allows ambiphilic behaviour to be observed, and X-ray diffraction analysis reveals dimeric arrangements for 2 and 3 with long intermolecular Zr-P bonds, whereas 4 remains monomeric in the solid state. DFT calculations indicate that the metal-phosphorus interaction is weak, and accordingly, complexes 2-4 act as monodentate ligands upon reaction with [W(CO)(5)(thf)]. The resulting complexes [W(CO)(5)(L)] 5-7 (L=2-4) were studied by IR spectroscopy and compared with the [W(CO)(5) ] complex 9, containing the phosphane-functionalised trozircene [(η(7)-C(7)H(7))Zr(η(5)-C(5)H(4)PPh(2))] (8). They all show a close resemblance to simple phosphanes, such as PMe(3) , although molecular orbital analysis of 2 reveals that the free electron pair in the phosphatrozircenes is not the HOMO. Four equivalents of 2 can replace 1,4-cyclooctadiene (COD) in [Ni(cod)(2)] to form the homoleptic, distorted tetrahedral complex [Ni{2}(4)] (10). 相似文献
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FAN Rui-qing ZHU Dong-sheng MU Ying LI Guang-Hua SU Qing NI Jian-guo FENG Shou-Hua 《高等学校化学研究》2005,21(4)
Introduction In the past decade, the imino-complexes based on late transition metal have received significantly increasing attention for their excellent performance in the olefin polymerization area since Brookhart et al.[1-8] 相似文献
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FANRui-qing ZHUDong-sheng MUYing LIGuang-hua SUQing NIJian-guo FENGShou-hua 《高等学校化学研究》2005,21(4):496-500
In the past decade, the imino-complexes based on late transition metal have received significantly increasing attention for their excellent performance in the olefin polymerization area since Brookhart et al. demonstrated that the Ni( Ⅱ ) complexes incorporating with sterically hindered α-diimine ligands could be used in the polymerization of ethylene to form high molecular weight polymers. 相似文献
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合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH3OH)](OTf)}n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH3OH}n(2)和[Cu(HL2)(CH3OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。 相似文献
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合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH3OH)](OTf)}n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH3OH}n(2)和[Cu(HL2)(CH3OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。 相似文献
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用具有低自旋d~B构型的[(NH_3)_5MIm]~(2+)(M=Co,Rh)和[(en)_2Co(Im)_2]~+为配体,与配位未饱和Zn的单核配合物作用,定向合成了5种新的含Zn咪唑桥联异双核、异三核配合物,并进行了元素分析、差热分析、摩尔电导及~1H NMR测定,确证了组成及咪唑桥的存在。 相似文献
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Manfred Scheer Peter Kramkowski Michael Schiffer Jan Müller 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):717-720
Herein we report the synthesis of different phosphido-complexes and -intermediates with WLE-triple bond. These compounds reveal different reactivity patterns. Details of reactivity as well as spectroscopic and theoretical aspects will be discussed in detail. 相似文献
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Two silver(I) complexes were prepared by the reaction of [Ag(C(CPh)]n with NP3 [NP3 = N(CH2CH2PPh2)3] or with NP3 and [Cu(CH3CN)4]ClO4. Complex 1 [(Ag2Cl(NP3)2)(Ag5(C(CPh)6)] contains both NP3 and PhC(C- ligands. The complex cation is (Ag2Cl(NP3)2)+, in which two Ag(NP3)+ cations were bridged by a Cl- donor. The anion is (Ag5(C(CPh)6)-, where five Ag+ ions are linked by six C(CPh- to form a pentanuclear cluster. Complex 2 only contains NP3 ligand, where the silver center adopts a trigonal-bipyramidal geometry. Crystal data for 1: C133H116Ag7Cl3N2P6, Mr = 2789.54, triclinic, space group P, a = 13.0780(2), b = 15.3678(2), c = 31.2041(3) (A), α = 91.3928(7), β = 90.9328(8), γ = 96.0244(4)o, V = 6233.8(1) (A)3, T = 293(2) K, Z = 2, Dc = 1.486 g/cm3, F(000) = 2796, μ = 1.266 mm-1, the final R = 0.0746 and wR = 0.1953 for 16475 observed reflections with I > 2σ(I). Crystal data for 2: C42H42AgClNO4P3, Mr = 861.00, trigonal, space group R3, a = 17.451(1), b = 17.451(1), c = 11.3985(7) (A), V = 3006.0(3) (A)3, T = 293(2) K, Z = 3, Dc = 1.427 g/cm3, F(000) = 1326, μ = 0.731 mm-1, the final R = 0.0251 and wR = 0.0663 for 1499 observed reflections with I > 2σ(I). 相似文献
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1 INTRODUCTION Great attention has currently been paid to com-pounds formed by the reaction between phosphineand metal alkynyl building blocks[1]. The ligand NP3contains one tertiary nitrogen atom as well as threephosphorous atoms and bonds to the metal ions as atetradentate ligand, affording tetrahedral[2] or triangle-bipyrimidal geometry[3, . In other coordination ca- 4]ses, one[5, , two[7], three P donors[8, 6] … 相似文献
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合成了4-硝基邻苯二硫酚配体及相应金属镍配合物,(Bu4N)2[Ni(nbdt)2]
(1)和(Bu4N)[Ni(nbdt)2] (2)(nbdt=4-硝基邻苯二硫酚阴离子), 并通过X-射线单晶结构测定、循环伏安、ESR谱、紫外可见吸收光谱和变温磁化率实验对其结构和性质进行了表征。这两个化合物均为略有变形的平面四方型配合物。配合物2是由配合物1通过I2氧化制备。配合物2含有一个未成对电子,磁性研究表明由于分子间的自旋耦合使它表现为反铁磁性。 相似文献
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过渡金属正离子和卡宾配合物成键特征的理论分析 总被引:4,自引:0,他引:4
在6—311C基组从头算的基础上对第一过渡系含偶数电子的金属正离子(Sc^+, V^+,Mn^+,Co^+,Cu^+)与卡宾CH2的配合物的成键特征进行了细致的分析。用能 级位移算符逐步降低分子片空轨道能级的方法代替分子片轨道冻结,使KSM能量分 解的耦合项得以消除。能量分析结果表明,Sc^+-CH2键是由σ供键,π供键与π反 馈键组成的,不能忽略π供键。而Cu^+-CH2键是由σ供键与σ,π反馈键组成的, 不能忽略σ反馈键。同时对VCH2^+,MnCH2^+和CoCH2^+的^1A1电子态也进行了粗略 的讨论。 相似文献
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Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition
metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities
for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex
catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition,
several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and
Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic
behavior with size-selective molecular recognition. 相似文献
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1 INTRODUCTION The polyaza macrocyclic and macrobicyclic mo-lecules have been extensively studied due to theirinclusion ability for neutral molecules, coordinationability for metal cations and versatile roles in thefields of recognition, transformation… 相似文献
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Qin Meng Guo-Ming Wang Huan He Bai-Feng Yang Guo-Yu Yang 《Journal of Cluster Science》2014,25(5):1295-1305
Two new pentaborates [M(dap)3][B5O6(OH)4]2·H2O (M = Co (1) and Ni (2); dap = 1,2-diaminopropane) have been hydrothermally synthesized. Both structures were determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence spectroscopy. Two compounds are isostructural and consist of isolated pentaborate [B5O6(OH)4]? anions and [M(dap)3]2+ complex cations. The anionic [B5O6(OH)4]? groups are linked by extensive hydrogen bonds to form a 3-D supramolecular framework with large channels, in which the transition-metal complex templates are located. The luminescent properties of 1 and 2 were studied, and blue luminescence occurs with an emission maximum at 405 and 408 nm upon excitation at 332 and 328 nm respectively. Crystal data: 1, monoclinic, space group P21/c (No. 14), a = 9.7159(5) Å, b = 29.3372(19) Å, c = 11.5121(6) Å, β = 103.286(5)°, V = 3193.6(3) Å3, Z = 4; 2, monoclinic, space group P21/c, a = 9.7264(4) Å, b = 29.3810(16) Å, c = 11.5185(6) Å, β = 103.249(4)°, V = 3204.0(3) Å3, Z = 4. 相似文献
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Aromatic compounds were efficiently nitrated under facile reaction conditions by employing 69% nitric acid catalyzed by transition-metal complexes such as [Co(NH3)5Cl]Cl2, [Cu(NH3)4]SO4, Mn(acac)3, [Ni(NH3)6]Cl2, [Ni(en)3]S2O3, and Hg[Co(SCN)4]. The reaction was completed smoothly at room temperature and afforded corresponding mono-nitro derivatives in quantitative yield. This new method offers efficient and facile regioselective mononitration of aromatic compounds.
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A. A. Karasik G. N. Nikonov R. Z. Musin Yu. Ya. Efremov 《Russian Chemical Bulletin》1992,41(1):167-169
The reaction of 2,5-diphenyl-1,3,2,5-dioxaboraphosphorinane (L) and 1,3,5-triphenyl-1,3,5-diazaphosphorinane (L) with molybdenum hexacarbonyl gave, respectively, Mo(CO)4L2 and Mo(CO)5L complexes.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 201–203, January, 1992. 相似文献