The Activation and Carbonylation of the C-Cl Bond Catalyzed by Transition-Metal Complexes

Thecarbonylationoforganichalides,catalyzedbytransition-metalcomPlexes,isareactionofindustrialinterestleadingtoawiderange0fproductslilieesters,aldehydes,awhdesandacids.Formanyyears,catalyticactivationandfunctionalisationofthecarbonthalogenbondsinorganichalideshavebeenoneofthemostchallengingproblemsanddesirablegoalsforchendsts.Oforganichalides,0rgancchlorideisthemodrmaforeundiDexPdrieerefD1thepeDfu3efulboinboLalindusny.However,because0ftheinertness0ftheirC-Clbonds,organicchloridesexhibitl0wre…     

Cycloheptatrienyl zirconium sandwich complexes with lewis basic phospholyl ligands (phosphatrozircenes): synthesis, structure, bonding and coordination chemistry

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).     

过渡金属配合物催化乙腈碳碳单键断裂的研究进展

有机化合物中的碳碳单键断裂反应是一类非常重要而且具有挑战性的反应,过去的几十年中,关于有机腈类化合物中碳碳单键的催化断裂反应研究受到了很多的关注。而乙腈作为常用的有机溶剂之一,其分子是有机腈类中的最小分子。本文结合最近几年国内外及本课题组关于乙腈分子的碳碳单键活化断裂的研究,综述了各类过渡金属配合物催化乙腈分子碳碳单键断裂的研究进展,分析了当前存在的问题,提出了对今后研究的展望。     

过渡金属配合物催化乙腈碳碳单键断裂的研究进展

有机化合物中的碳碳单键断裂反应是一类非常重要而且具有挑战性的反应,过去的几十年中,关于有机腈类化合物中碳碳单键的催化断裂反应研究受到了很多的关注。而乙腈作为常用的有机溶剂之一,其分子是有机腈类中的最小分子。本文结合最近几年国内外及本课题组关于乙腈分子的碳碳单键活化断裂的研究,综述了各类过渡金属配合物催化乙腈分子碳碳单键断裂的研究进展,分析了当前存在的问题,提出了对今后研究的展望。     

Syntheses, Characterization and Crystal Structures of New Nickel Complexes with 2,6-Bis(imino)pyridyl Ligands

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]     

Syntheses, Characterization and Crystal Structures of New Nickel Complexes with 2,6-Bis （ imino ） pyridyl Ligands

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.     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

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。     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

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。     

含Zn咪唑桥联异多核配合物的合成与表征

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。     

Complexes with a Metal Phosphorus Triple Bond

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.     

Syntheses and Crystal Structures of Silver(I) Complexes by Depolymerizing [Ag(C(CPh)]n with a NP3 Ligand

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).     

Syntheses and Crystal Structures of Silver(I) Complexes by Depolymerizing [Ag(C≡CPh)]_n with a NP_3 Ligand

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] …     

4-硝基邻苯二硫酚金属镍配合物的合成、结构和性质

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。     

过渡金属正离子和卡宾配合物成键特征的理论分析

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。     

Transition-Metal Complexes with Nano-Sized Phosphine and Pyridine Ligands-Catalysis,Fluxional Behavior and Molecular Recognition

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.     

Syntheses and Crystal Structures of Two Silver(I) Complexes Isolated by the Reaction of [Ag(PPh3)2(MeCN)](SbF6) with a N6 Ligand

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…     

Syntheses and Crystal Structures of Two New Pentaborates Templated by Transition-Metal Complexes

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) ų, 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) ų, Z = 4.     

Mild and Efficient Nitration of Aromatic Compounds Mediated by Transition-Metal Complexes

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.

Complexes of 2,5-diphenyl-1,3,2,5-dioxaboraphosphorinane and 1,3,5-triphenyl-1,3,5-diazaphosphorinane with molybdenum hexacarbonyl

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.