Lanthanide amides [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) catalyzed hydrophosphonylation of aryl aldehydes

A highly efficient method for the synthesis of α-hydroxy phosphonates via lanthanide amides [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) catalyzed hydrophosphonylation of aromatic aldehydes was developed. The reactions produced the products in excellent yields in the presence of 0.1 mol % [(Me(3)Si)(2)N](3)La(μ-Cl)Li(THF)(3) at room temperature within 5 min. The existence of LiCl in the catalyst was a key factor affecting the catalytic activity. The mechanism for the process of high efficiency was proposed.     

有机镧系络合物[Li(THF)2]2(μ-Cl)4(η^5-C5H5)Ln.THF的合成

Manastyrskyj 等首次报道了重稀土环戊二烯二氯化物 C_5H_5L_nC(?)_2(Ln=Sm～Lu)的合成,但未得到相应的轻稀土环戊二烯基二氯化物。他们把这一结果归因于镧系收缩和配位不     

[Flu(Me)2CCp]2Yb(μ-Br)2Li(THF)2·THF的合成和晶体结构

为考察取代环戊二烯基或桥联环戊二烯基有机稀土化合物的性质,研究了碳桥联芴基环戊二烯基配体与卤化稀土的反应,其中,[2-(9-芴基)异丙基]环戊二烯基锂[Flu(Me)2CCpLi]与三溴化镱(YbBr3)在四氢呋喃(THF)中反应,分离得到了标题配合物[Flu(Me)2CCp]2Yb(μ-Br)2Li(THF)2·THF.X射线单晶结构测定表明配合物属单斜晶系,空间群为P2(1)/n,晶胞参数为a=1.4676(3) nm,b=1.2618(4) nm,c=2.9736(9) nm,β=98.172(18)°,Z=4,V=5.451(2) nm3,Mr=1098.84,Dc=1.339 mg·m-3,R=0.0695,wR=0.1721.中心Yb原子分别与两个环戊二烯基和两个溴原子成键,形成扭曲的四面体配位构型.Yb-Br1和Yb-Br2键长分别为0.2765(1)和 0.2738(1) nm,两个环戊二烯基平面的夹角为125.7°,中心Yb原子与两个环戊二烯基环中心的平均距离分别为0.232和0.231 nm.     

Guanidinate borohydride derivatives of lanthanides: synthesis and molecular structures of the [(Me3Si)2NC(NCy)2]Gd(BH4)2DME and [{(Me3Si)2NC(NPri)2}2Sm(BH4)2]−[Li(DME)3]+ complexes. Catalytic activity of the [(Me3Si)2NC(NCy)2]2Ln(BH4)2Li(THF)2 complexes (Ln = Nd, Sm, or Yb) in methyl methacrylate polymerization

The reaction of Gd(BH₄)₃(THF)₂ with two equivalents of sodium N,N′-dicyclohexyl-N″-bis(trimethylsilyl)guanidinate in THF followed by the treatment of the reaction product with 1,2-dimethoxyethane produced the monoguanidinate bis(borohydride) complex [(Me₃Si)₂NC(NCy)₂]Gd(BH₄)₂DME (1) (Cy is cyclohexyl). The treatment of the heterobimetallic samarium complex {(Me₃Si)₂NC(NPrⁱ)₂}₂Sm(BH₄)₂Li(THF)₂, in which the lanthanide and lithium atoms are linked by two bridging borohydride groups, with 1,2-dimethoxyethane afforded the ionic complex [{(Me₃Si)₂NC(NPrⁱ)₂}₂Sm(BH₄)₂]^?[Li(DME)₃]⁺ (2). The structures of complexes 1 and 2 were established by X-ray diffraction. The [(Me₃Si)₂NC(NCy)₂]₂Ln(BH₄)₂Li(THF)₂ complexes (Ln = Nd (3), Sm (4), or Yb (5)) were found to catalyze methyl methacrylate polymerization.     

Mixed-ligand guanidinate derivatives of rare-earth metals. Molecular structures of { (Me3Si)2NC(N-cyclo-Hex)2}Y[N(SiMe3)2]2, [{ (Me3Si)2NC(N-cyclo-Hex)2}YbI(THF)2]2, and [{(Me3Si)2N} Y(THF)(µ-Cl)]2 complexes

The insertion of N,N′-dicyclohexylcarbodiimide at one of the Y-N bonds of the [(Me₃Si)₂N]₃Y complex in toluene at 70 °C afforded the monoguanidinate diamide derivative { (Me₃Si)₂NC(N-cyclo-Hex)₂}Y[N(SiMe)₃]₂ (1) (cyclo-Hex is cyclohexyl) in 72% yield. The reaction of equimolar amounts of sodium N,N′-dicyclohexyl-N″-bis(trimethylsilyl)guanidinate, which was prepared in situ from {(Me₃Si)₂N}Na and N,N′-dicyclohexylcarbodiimide, and YbI₂(THF)₂ in THF gave the [{(Me₃Si)₂NC(N-cyclo-Hex)₂}YbI(THF)₂]₂ complex (2). An attempt to use this procedure for the synthesis of the yttrium compound { (Me₃Si)₂NC(NSiMe₃)₂}₂YCl containing the sterically more hindered guanidinate ligand unexpectedly led to the formation of the diamide chloride complex [{(Me₃Si)₂N}₂Y(THF)(µ-Cl)]₂ (3). The structures of complexes 1–3 were established by X-ray diffraction. Compound 1 is mononuclear. Complexes 2 and 3 are dinuclear and contain two µ²-bridging halide ligands.     

Bulk polymerization of rac-lactide initiated by guanidinate alkoxide complexes of rare earth metals. The molecular structure of the cluster [{(Me3Si)2NC(NPri)2}Nd]4(μ3-OPri)8Li7(μ2-Cl)3(μ3-Cl)2(μ4-Cl)2

The complexes {(Me₃Si)₂NC(NPrⁱ)₂}₂LnOBu^t (Ln = Y (1), Lu (2)) initiate the bulk polymerization of racemic lactide (LA) at 130 °C. At the monomer: initiator molar ratio ([LA]: 1) equal to 1000: 1, the quantitative conversion of the monomer is achieved within 6 h. The resulting polymers are characterized by a rather narrow monomodal molecular weight distribution (M _w/M _n = 1.46–1.82) and molecular weights up to 33400 g mol^?1. The molecular weights of the resulting polylactides measured by gel permeation chromatography are 3–11 times lower than the values calculated from the monomer: initiator ratio on the assumption of one growing polymer chain per catalytic center. The reaction of the in-situ prepared complex [(Me₃Si)₂NC(NPrⁱ)₂]NdCl₂ with 2 equiv. of PrⁱOLi produced the 11-nuclear cluster [{(Me₃Si)₂NC(NPrⁱ)₂}Nd]₄(μ³-OPrⁱ)₈Li₇(μ²-Cl)₃(μ³-Cl)₂(μ⁴-Cl)₂ (3), which was isolated in 62% yield. The structure of compound 3 was established by X-ray diffraction. Complex 3 initiates both the bulk and solution polymerization of rac-lactide. In the bulk polymerization at the molar ratio [LA]: [Nd] = 500: 1, the 89% conversion of the monomer was achieved within one hour. The polylactide thus synthesized has the molecular weight M _n = 19720 g mol^?1 and a rather narrow polydispersity M _w/M _n = 1.54.     

[(O)MoCu_3(μ_3-S)_3(μ_3-Cl)(PPh_3)_3]·2THF的合成及其晶体结构

固体化合物(NH_4)_6Mo_7O_(24)·4H_2O和(PPh_3)_2CuCl与饱和液体NH_4HS反应获得桔红针状标题晶体。晶体空间群为P2_1/c,晶胞参数a=11.742(2),b=28.186(7),c=19.304(3),β=100.57(2)°,V=6280.4(?)~3,D_c=1.46g/cm~3,Z=4,F(000)=2816。在3≤2θ≤45°范围内收集到8414个独立衍射强度数据,其中3856个I≥1.5σ(I)强度数据参加结构计算。标题化合物分子是以{MoCu_3S_3Cl}类立方烷型簇为核心的分子,Mo—Cu的平均距离为2.716。     

Synthesis and molecular structure of [1, 3-(Me3Si)2C5H3]2Lu(μ-Cl)2

Cp^* ₂Lu(-Cl)₂ (1) was isolated following the reaction of Cp^*Na (Cp^* = 1, 3-(Me₃Si)₂C₅H₃) with LuCl₃ in THF and subsequent treatment with toluene at 80°C. An X-ray structural investigation of1 was performed (MoK radiation, 2933 reflections,R = 0.020). The crystals are triclinic,a = 10.744(3) Å,b=11.821(2) Å, c=12.966(3) Å, a=71.54(1)°, =85.32(2)°, =74.83(1)°,Z = 2, space groupP-1. Two Lu atoms withdistorted tetrahedral coordination are linked by two chloride bridges with a mean Lu-Cl distance equal to 2.62 Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1993.     

[Ph(Me3Si)N]3Yb(THF)的合成及其催化Tischenko反应的研究

通过无水YbCl3和Ph[(CH3)3N]Li在四氢呋喃中反应,合成了目标化合物[Ph(Me3Si)N]3Yb(THF),该化合物经过元素分析,红外光谱以及X单晶结构表征.研究表明该配合物以较高活性催化芳醛的Tischenko反应.     

Lanthanide amides [(Me3Si)2N]3Ln(µ‐Cl)Li(THF)3‐catalyzed phospho‐aldol‐brook rearrangement reaction of dialkyl phosphites with isatins

The tetracoordinated lanthanide amides [(Me₃Si)₂N]₃Ln(µ‐Cl)Li(THF)₃ were found to serve as highly active catalysts for the phospho‐Aldol‐Brook rearrangement reaction of various dialkyl phosphites and isatins. The reactions produced dialkyl 2‐oxoindolin‐3‐yl phosphates in good to excellent yields in the presence of 1 mol% [(Me₃Si)₂N]₃La(µ‐Cl)Li(THF)₃ at room temperature within 5 min. A mechanism for this highly efficient process was proposed. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:449–456, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21036     

Synthesis of Substituted Indenyl Lanthanide Chloride and Molecular Structure of[（C5H9C9H6）2Yb（μ—Cl）2Li（Et2O）2]

Reaction of anhydrous ytterbium trichlorides with 2 equiv.of cyclopentylindenyl lithium in THF solution,followed by removal of the solvent and crystallization of the porduct from diethyl ether,affords a crystal complex of the composition(C5H9C9H6)2Yb(μ-Cl)2Li(Et2O)2.Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenly rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb,Li and two chlorine atoms form a plane.     

A Novel Divalent Ytterbium Complex Supported by a Bridged Diamide Ligand: Synthesis and Structure of [{Me2Si(NPh)2Yb(THF)2}(μ3‐Cl)(μ4‐Cl){Li(THF)}2]2·2THF

The reaction of anhydrous YbCl₃ with 1 equiv. of Li₂Me₂Si(NPh)₂ in THF, after workup, yielded a ytterbium(III) chloride [{Me₂Si(NPh)₂Yb}(μ₂‐Cl)(TMEDA)]₂·3PhMe ( 1 ) (TMEDA=tetramethylethanediamine). The same reaction followed by treatment with Na‐K alloy afforded a new ytterbium(II) complex supported by a bridged diamide with four coordinated LiCl molecules, [{Me₂Si(NPh)₂Yb(THF)₂}(μ₃‐Cl)(μ₄‐Cl){Li(THF)}₂]₂·2THF ( 2 ) in high yield. Both complexes were structurally characterized by X‐ray analysis to be dimers. Complex 1 was a chlorine‐bridged dimer with ytterbium in a distorted octahedral geometry. In complex 2 two [Me₂Si(NPh)₂Yb(THF)₂]‐(μ₃‐Cl)[Li(THF)]₂ moieties were connected with each other by two μ₄‐Cl bridges to form a "chair‐form" framework.     

An Efficient Synthesis of 1,5-Benzodiazepine Derivatives by Lanthanide Trichloride-catalyzed Condensation of o-Phenylenediamine with α,β-Unsaturated Ketone under Mild Conditions

三氯化稀土有效地催化了邻苯二胺与一系列α,β-不饱和酮的反应,在温和条件下以中等到高的收率生成1,5-苯并二氮杂卓。     

中性均配型稀土胺化物Yb(NPh_2)_3(THF)_2的合成、表征及晶体结构

无水YbCl3与三倍量的LiNPh2 在四氢呋喃 (THF)中反应 ,合成了中性均配型稀土胺化物Yb(NPh2 ) 3(THF) 2 。产物经元素分析、红外光谱表征 ,并测定了其晶体结构。配合物属单斜晶系 ,P2 1 /n空间群 ,晶胞参数为a =1 2 0 5 2 ( 2 )nm ,b =1 9369( 3)nm ,c =1 65 2 3( 2 )nm ,β =92 79( 1)°,V =3 85 2 4( 9)nm3,Z =4,Dc=1 417g·cm- 3,μ =2 4 67cm- 1 (MoKα) ,F( 0 0 0 ) =1668,R =0 0 36,Rw=0 0 39。3个二苯胺基的氮原子和两个THF的氧原子与金属镱配位 ,形成五配位的扭曲的三角双锥几何构型。平均的Yb—N键长为 0 2 2 19( 6)nm。     

Activation of SO2 with [(η5‐C5Me5)2Ln(THF)2] (Ln=Eu,Yb) Leading to Dithionite and Sulfinate Complexes

The reaction of decamethylytterbocene [(η⁵‐C₅Me₅)₂Yb(THF)₂] with SO₂ at low temperature gave two new compounds, namely, the Yb^III dithionite/sulfinate complex [{(η⁵‐C₅Me₅)₂Yb(μ₃,1κ²O^1,3,2κ³O^2,2′,4‐S₂O₄)}₂{(η⁵‐C₅Me₅)Yb(μ,1κO,2κO′‐C₅Me₅SO₂)}₂] ( 1 ) and the Yb^III dithionite complex [{(η⁵‐C₅Me₅)₂Yb}₂(μ,1κ²O^1,3,2κ²O^2,4‐S₂O₄)] ( 2 ). After extraction of 1 , the mixture was heated to give the dinuclear tetrasulfinate complex [{(η⁵‐C₅Me₅)Yb}₂(μ,κO,κO’‐C₅Me₅SO₂)₄] ( 3 a ). In contrast, from the reaction of [(η⁵‐C₅Me₅)₂Eu(THF)₂] with SO₂ only the tetrasulfinate complex [{(η⁵‐C₅Me₅)Eu}₂(μ,κO,κO’‐C₅Me₅SO₂)₄] ( 3 b ) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO₂ molecules to form the dithionite anion S₂O₄^2?; and 2) nucleophilic attack of one metallocene C₅Me₅ ligand on the sulfur atom of SO₂. The compounds presented are the first dithionite and sulfinate complexes of the f‐elements.     

Direct Catalytic Asymmetric Mannich‐Type Reaction of α‐N3 Amide

An α‐N₃ 7‐azaindoline amide serves as a latent enolate to directly engage in an asymmetric Mannich‐type reaction with N‐thiophosphinoyl imines by the action of a cooperative catalyst. The thus‐obtained highly enantioenriched anti‐adduct was transformed into β‐amino‐α‐azido acid in high yield by simple acidic treatment.     

多核烷氧基簇合物Ln2Na8(OCH2CH2NMe2)12(OH)2作为均相催化剂催化Tishchenko反应

多核烷氧基稀土碱金属簇合物Ln2Na8(OCH2CH2NMe2)12(OH)2对Tishchenko反应显示良好的催化活性,高效催化一系列醛的二聚反应生成相应的酯。本文考察了多种因素对该催化反应活性的影响,并提出了可能的反应机理。     

Synthese und Struktur der Komplexe [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 und [(n‐Bu)4N]2[Pd3Cl8]

Synthesis and Crystal Structure of the Complexes [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂PdCl₂], [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ and [(n‐Bu)₄N]₂[Pd₃Cl₈] The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂ PdCl₂] ( 1 ) is obtained in THF by the reaction of PdCl₂(NCC₆H₅)₂ with [(n‐Bu)₄N][ReNCl₄] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl₂ instead of PdCl₂(NCC₆H₅)₂, orange crystals of hitherto unknown [(n‐Bu)₄N]₂[Pd₃Cl₈] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl₄Re≡N}₂PdCl₂]^2— a linear PdCl₂ moiety is connected in trans arrangement with two complex fragments [(THF)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd₃Cl₈]^2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph₄P][ReNCl₄] and PdCl₂(NCC₆H₅)₂ in THF brown crystals of the heterometallic complex, [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ ( 2 ) result. 2 crystallizes in the monoclinic space group P2₁/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)₂PdCl of the centrosymmetric anionic complex [(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂^2— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl₄Re≡N]^— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm.