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1.
Song Yang XianCui Zhu ShuangLiu Zhou ShaoWu Wang ZhiJun Feng Yun Wei Hui Miao LiPing Guo FenHua Wang GuangChao Zhang XiaoXia Gu XiaoLong Mu 《中国科学:化学(英文版)》2014,57(8):1090-1097
<正>1 Representation of complexes and selected bond distances and bond angles Figure S1 Structure of complex 4. Hydrogen atoms were omitted for clarity, ellipsoids set at the 30% probability level. Selected bond distances() and angles(°): Er(1)–Cl(1) 2.6180(18), Er(1)–N(1) 2.301(6), Er(1)–N(4) 2.232(6), Er(1)–N(5) 2.229(6), N(1)–Er(1)–Cl(1) 87.41(14), N(4)–Er(1)–Cl(1) 101.16(14), N(5)–Er(1)–Cl(1) 118.60(16), N(4)–Er(1)–N(1) 114.1(2), N(5)–Er(1)–N(1) 108.7(2), N(5)–Er(1)–N(4) 121.9(2).Figure S2 Structure of complex 5. Hydrogen atoms were omitted for clarity, ellipsoids set at the 30% probability level. Selected bond distances(o) and angles(°): Y(1)–Cl(1) 2.6212(12), Y(1)–N(1) 2.280(3), Y(1)–N(4) 2.214(3), Y(1)–N(5) 2.228(3), N(1)–Y(1)–Cl(1) 87.67(8), N(4)–Y(1)–Cl(1) 121.32(8), N(5)–Y(1)–Cl(1) 102.88(8), N(4)–Y(1)–N(1) 107.75(11), N(5)–Y(1)–N(1) 111.64(11), N(4)–Y(1)–N(5) 120.78(10). 相似文献
2.
Herbert Schumann Mario Glanz Esther C. E. Rosenthal Holger Hemling 《无机化学与普通化学杂志》1996,622(11):1865-1870
Organometallic Compounds of the Lanthanides. 113. [(tert-Butylcyclopentadienyl)(cyclopentadienyl)dimethylsilane] Complexes of selected Lanthanides The reaction of [Me2Si(C5H4)(tBuC5H3)]Li2 with LnCl3 (Ln = Y, Nd, Sm, Lu) in THF results in the formation of the chiral, dimeric complexes [Me2Si(C5H4)(tBuC5H3)]Ln(μ-Cl)2Li(THF)(Et2O) [Ln = Y ( 1 ), Nd ( 2 ), Sm ( 3 ), Lu ( 4 )]. The 1H-, 13C-NMR- and the mass spectra of the new compounds as well as the X-ray crystal structures of 2 a and 3 a were discussed. 相似文献
3.
The mono(guanidinate) lanthanide borohydride complexes of [(Me3Si)2NC(NCy)2]Ln(BH4)2(THF)2 (Ln = Yb (1), Er (2)) have been synthesized by the reactions of corresponding Ln(BH4)3(THF)3 with sodium guanidinate of [(Me3Si)2NC(NCy)2]Na in a 1:1 molar ratio in THF. They were characterized by elemental analysis, infrared spectrum and X-ray diffraction analysis. 1 and 2 have similar structures. The lanthanide ion was bonded by an η2-guanidinate ligand, two η3-BH4 ligands and two THF molecules as a distorted octahedron. The two BH4 ligands in a complex are equivalent and cis to each other. The structure of solvated sodium guanidinate of {[(Me3Si)2NC(NCy)2]Na(THF)}2 (3) was also presented. In a dimeric molecule of 3, each Na atom is bound to three nitrogen atoms from two guanidinate groups and one oxygen atom from the THF molecule. 1 and 2 displayed moderate high catalytic activity for the polymerization of methyl methacrylate. The Er complex is more active than the Yb complex. 相似文献
4.
N-Silylation and Si? O Bond Splitting at the Reaction of Lithiated Siloxy-silylamino-silanes with Chlorotrimethylsilane Lithiated Siloxy-silylamino-silanes were allowed to react in tetrahydrofurane (THF) and in n-octane (favoured) and n-hexane, resp., with chlorotrimethylsilane. The monoamide (Me3SiO)Me2Si(NLiSiMe3) gives in THF and in n-octane the N-substitution product (Me3SiO)Me2Si · [N(SiMe3)2] 1 , the diamide (Me3SiO)MeSi(NLiSiMe3)2 only in THF the N-substitution products (Me3SiO)MeSi[N(SiMe3)2]2 2 (main product) and (Me3SiO)MeSi[N(SiMe3)2](NHSiMe3) 3 . In n-octane the diamide reacts mainly under Si? O bond splitting. The cyclodisilazane [(Me3SiNH)MeSi? NSiMe3]2 6 is obtained as the main product. Byproducts are 2, 3 and the tris(trimethylsilylamino) substituted disilazane (Me3SiO)(Me3SiNH)MeSi? N · (SiMe3)? SiMe(NHSiMe3)2 7 . The triamide (Me3SiO)Si · (NLiSiMe3)3 reacts under Si? O and Si? N bond splitting in n-octane as well as in THF. The cyclodisilazanes [(Me3SiNH)2 · Si? NSiMe3]2 10 and ( 11 : R = Me3SiNH, 12 : R = (Me3Si)2N) are formed. in THF furthermore the N-substitution products (Me3SiO)Si[N(SiMe3)2] · (NHSiMe3)2 4 and (Me3SiO)Si[N(SiMe3)2]2(NHSiMe3) 5 . The Si? O bond splitting occurs in boiling n-octane also in absence of the chlorotrimethylsilane. An amide solution of (Me3SiO)MeSi(NHSiMe3)2 with n-butyllithium in the molar ratio 1 : 1 leads in n-octane and n-hexane to 6 and 7 , in THF to 3 . The amide solutions of (Me3SiO)Si · (NHSiMe3)3 with n-butyllithium the molar ratio 1 : 1 and 1 : 2 give in THF 4 and 5 , respectively. 相似文献
5.
Jun Du Shuangliu Zhou Xiuli Zhang Lijun Zhang Peng Cui Zeming Huang Yun Wei Xiancui Zhu Shaowu Wang 《应用有机金属化学》2020,34(1):e5275
Reactions of the ligand precursors 2-(2′-pyridyl)-3,5-Me2-pyrrole ( L 1 H) and 2-(2-pyridyl)-3,4,5-Me3-pyrrole ( L 2 H) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of low-coordinated rare-earth metal bis-amido complexes L 1 RE[N(SiMe3)2]2 [RE = Y ( 1a ), Dy ( 1b ), Er ( 1c ), Yb ( 1d )] and L 2 RE[N(SiMe3)2]2 [RE = Y ( 2a ), Dy ( 2b ), Er ( 2c ), Yb ( 2d )]. With the ionic radius of rare-earth metal increasing, the reaction of L 1 H and [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 gave dinuclear complexes ( L 1 )2RE(μ-Cl)(μ-η5:η1:η1- L 1 )RE( L 1 )[N(SiMe3)2]2 [RE = Sm ( 1e ), Pr ( 1f )]; however, the reaction of L 2 H and [(Me3Si)2N]3Sm(μ-Cl)Li(THF)3 afforded ( L 2 )2Sm[N(SiMe3)2]2 ( 2e ). Results indicated that the ionic radius of rare-earth metal and subtle change in the ligands have substantial effects on the structure and bonding mode of complexes. The complexes showed a high catalytic activity for the ring-opening reaction of cyclohexene oxide with amines to afford various β-aminoalcohols under mild solvent-free conditions. 相似文献
6.
G. G. Skvortsov M. V. Yakovenko G. K. Fukin A. V. Cherkasov A. A. Trifonov 《Russian Chemical Bulletin》2007,56(9):1742-1748
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. 相似文献
7.
The trichlorides of yttrium, samarium, and lutetium react with 2 equivalents of Na[C5H4 tBu] and 1 equivalent of NaBH4 to give [(η5-C5H4 tBu)2LnBH4(THF)] (Ln = Y ( 1 ), Sm ( 2 ), Lu ( 3 )) or with 2 equivalents of Na[C5Me4R] and 1 equivalent of NaBH4 to form [(η5-C5Me4R)2 · LnBH4(THF)] (R = H, Ln = Y ( 4 ), Sm ( 5 ), Lu ( 6 ); R = Me, Ln = Y ( 7 ), Sm ( 8 ), Lu ( 9 ); R = Et, Ln = Y ( 10 ), Sm ( 11 ), Lu ( 12 ); R = iPr, Ln = Y ( 13 ), Sm ( 14 ), Lu ( 15 )). The new compounds have been characterized by elemental analysis, NMR spectroscopy and mass spectrometry. The crystal structures of 8 and 10 were determined by single crystal X-ray diffraction. 相似文献
8.
Delphine Prvot Christophe Galliot Anne-Marie Caminade Jean Pierre Majoral 《Heteroatom Chemistry》1995,6(4):313-318
Phosphorus dialdehydes RP (OC6H4CHO)2 (R = Ph, Me2N) react with phosphodihydrazides PhP(Y)-[N(CH3)NH2]2 (Y = S, O) to give macrocycles 6a–c arising from [2 + 2] cyclocondensation reactions. Treatment of phosphodihydrazone PhP(S) [OC6H4CH N–N(Me)H]2 7 with phenyldichlorophosphine affords macrocycle 8 possessing tri and tetracoordinated phosphorus atoms. Clean desulfurization of thiophosphorus macrocycles 9 and 12 gives rise selectively to new tricoordinated phosphorus containing macrocycles 11 and 13 . 相似文献
9.
Rare‐Earth‐Metal Methyl,Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand
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Dorothea Schädle Dr. Cäcilia Maichle‐Mössmer Dr. Christoph Schädle Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):662-670
The reaction of monomeric [(TptBu,Me)LuMe2] (TptBu,Me=tris(3‐Me‐5‐tBu‐pyrazolyl)borate) with primary aliphatic amines H2NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(TptBu,Me)LuMe(NHR)], the solid‐state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(TptBu,Me)LnMe({μ2‐Me}AlMe3)] (Ln=Y, Ho) reacted selectively and in high yield with H2NR, according to methane elimination, to afford heterobimetallic complexes: [(TptBu,Me)Ln({μ2‐Me}AlMe2)(μ2‐NR)] (Ln=Y, Ho). X‐ray structure analyses revealed that the monomeric alkylaluminum‐supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by 1H and 13C NMR spectroscopic studies at variable temperatures and 1H–89Y HSQC NMR spectroscopy. Treatment of [(TptBu,Me)LnMe(AlMe4)] with H2NtBu gave dimethyl compounds [(TptBu,Me)LnMe2] as minor side products for the mid‐sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative‐scale amounts of complexes [(TptBu,Me)LnMe2] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(TptBu,Me)LnMe(AlMe4)] with N,N,N′,N′‐tetramethylethylenediamine (tmeda). The solid‐state structures of [(TptBu,Me)HoMe(AlMe4)] and [(TptBu,Me)HoMe2] were analyzed by XRD. 相似文献
10.
Herbert Schumann Jrn Winterfeld Esther C. E. Rosenthal Holger Hemling Lothar Esser 《无机化学与普通化学杂志》1995,621(1):122-130
Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)], and [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] A series of lanthanide(III) amides [Ln{N(C6H5) · (SiMe3)}3(THF)x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl3, with LiN(C6H5)(SiMe3). Treatment of NdCl3(THF)2 and LuCl3(THF)3 with the lithium salts of the bulky amides [N(C6H3R2-2,6)(SiMe3)]? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2, 6)(SiMe3)}2(THF)] ( 11 ) and [ClLn{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The 1H- and 13C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed. 相似文献
11.
Michael R. Kunze Dirk Steinborn Kurt Merzweiler Christoph Wagner Joachim Sieler Rudolf Taube Prof. Dr. 《无机化学与普通化学杂志》2007,633(9):1451-1463
The tris(2,4‐dimethylpentadienyl) complexes [Ln(η5‐Me2C5H5)3] (Ln = Nd, La, Y) are obtained analytically pure by reaction of the tribromides LnBr3·nTHF with the potassium compound K(Me2C5H5)(thf)n in THF in good yields. The structural characterization is carried out by X‐ray crystal structure analysis and NMR‐spectroscopically. The tris complexes can be transformed into the dimeric bis(2,4‐dimethylpentadienyl) complexes [Ln2(η5‐Me2C5H5)4X2] (Ln, X: Nd, Cl, Br, I; La, Br, I; Y, Br) by reaction with the trihalides THF solvates in the molar ratio 2:1 in toluene. Structure and bonding conditions are determined for selected compounds by X‐ray crystal structure analysis and NMR‐spectroscopically in general. The dimer‐monomer equilibrium existing in solution was investigated NMR‐spectroscopically in dependence of the donor strength of the solvent and could be established also by preparation of the corresponding monomer neutral ligand complexes [Ln(η5‐Me2C5H5)2X(L)] (Ln, X, L: Nd, Br, py; La, Cl, thf; Br, py; Y, Br, thf). Finally the possibilities for preparation of mono(2,4‐dimethylpentadienyl)lanthanoid(III)‐dibromid complexes are shown and the hexameric structure of the lanthanum complex [La6(η5‐Me2C5H5)6Br12(thf)4] is proved by X‐ray crystal structure analysis. 相似文献
12.
A. A. Trifonov D. M. Lyubov E. A. Fedorova G. G. Skvortsov G. K. Fukin Yu. A. Kurskii M. N. Bochkarev 《Russian Chemical Bulletin》2006,55(3):435-441
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. 相似文献
13.
Herbert Schumann Jrn Winterfeld Markus R. Keitsch Katja Herrmann Jrg Demtschuk 《无机化学与普通化学杂志》1996,622(9):1457-1461
Organometallic Compounds of the Lanthanoids. 111. Synthesis and Characterization of Cationic Metallocene Complexes of the Lanthanoides. X-Ray Crystal Structure of [Cp Yb(THF)2][BPh4] Cationic organolanthanoide compounds [(C5H4R)2Sm(THF)2][BPh4] (R = tBu ( 1 ), SiMe3 ( 2 )), [PyrSm(THF)][BPh4] ( 3 ) (Pyr* = NC4H2tBu2-2,5), [CpLn(THF)2][BPh4] (Cp* = C5Me5; Ln = Y ( 4 ), Yb ( 5 )), and [(C5Me4Et)2 Ln(THF)2][BPh4] (Ln = Y ( 6 ), Sm ( 7 )) have been synthesized by oxidation of the divalent metallocenes [(C5H4R)2Sm(THF)2] (R = tBu, SiMe3), [PyrSm(THF)], [CpYb(THF), and [(C5Me4Et)2Sm(THF)] with Ag[BPh4] and by protolysis of the lanthanoide alkyls [CpYMe(THF)], [CpYbCH(SiMe3)2], and [(C5Me4Et)2LnCH(SiMe3)2] (Ln = Y, Sm) by [NEt3H][BPh4]. The 1H- and 13C-NMR spectra of the new compounds are discussed. 5 crystallizes in the space group P21/c with a = 10.604(7), b = 21.749(3), c = 19.124(4) Å, β = 96.47(4)°, Z = 4 and V = 4383(3) Å3 (R = 0.0291 for 8517 observed reflections with Fo ≥ 4σ (Fo). 相似文献
14.
Fengfu Li Yingtai Jin Chunlei Song Yonghua Lin Fengkui Pei Fosong Wang Ninghai Hu 《应用有机金属化学》1996,10(10):761-771
Three new lanthanide (Ln)–alkylaluminium (Al) bimetallic complexes with the formula [(μ-CF3CO2)2Ln(μ-CF3CHO2)AlR2 · 2THF]2 (Ln=Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF3CO2)3 (Ln=Nd, Y) with HAl (i-Bu)2 and of Eu(CF3CO2)3 with AlEt3, respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(μ-CF3CO2)2Nd (μ-CF3CHO2)Al(i-Bu)2 · 2THF]2 (Nd–Al) and [(μ-CF3CO2)2Y(μ-CF3CHO2)Al(i- Bu)2 · 2THF]2 (Y–Al) are isomorphous and crystallize in space group P 1 with a =12.441(3) Å [12.347(5) Å for Y–Al], b =12.832(3) Å [12.832(4) Å], c =11.334(3) Å [11.292(8) Å], α=104.93 (2)° [104.45(4)°], β=98.47(2)° [98.81(4)°], γ=64.60(2)° [64.30(3)°], R =0.519 [0.113], R w=0.0532 [0.110], Z =1 and [(μ-CF3CO2)2Eu(CF3 CHO2)AlEt2 · 2THF]2(Eu–Al) in space group P 21/ n with a =11.913(6) Å, b =14.051(9) Å, c =17.920(9) Å, α=101.88(11)°, β=γ=90°, R =0.0509, R w=0.0471 and Z =2. The six CF3CO 相似文献
15.
《Journal of organometallic chemistry》1994,481(2):275-282
The mixed sandwich complexes [(C8H8)Ln(C5Me4Et)(THF)x] (Ln = Y 1, La 2, Nd 3, Sm 4, Gd 5, Tm 6, Lu 7), [(C8H8)Ln{C5H2(SiMe3)3}(THF)x (Ln = Pr 8, Dy 9) and [(C8H8)Pr(C5Ph5)] (10), have been prepared by the metathetic reaction of [(C8H8)Ln(μ-Cl)-(THF)n]2 with NaC5Me4Et, LiC5H2(SiMe3)3 and NaC5Ph5 in THF. The 1:2 reaction of 7 with acetylacetone results in displacement of the (C8H8)-ligand to generate the new complex [(C5Me4Et)Ln(acac)2] (acac = [CH3C(O)CHC(O)CH3]−) (11). The molecular structures of 7 (monoclinic space group P21/c with a = 990.4(5) pm, b = 1228.2(5) pm, c = 2757.5(16) pm, β = 93.92(4)°, V = 3346(3)·10−30 m3 and Z = 8) and 11 (triclinic space group P1̄ with a = 957.3(3) pm, b = 1064.5(2) pm, c = 1068.3(2) pm, α = 94.19(12)°, β = 96.37(17)°, γ = 96.71(16)°, V = 1070.3(4)·10−30 m3 and Z = 2) have been determined by X-ray diffraction. 相似文献
16.
Organometallic Compounds of the Lanthanides. 133 Synthesis and Characterization of donor-functionalised ansa -Metallocenes of Yttrium, Neodymium, Samarium, Erbium, and Lutetium The reaction of Me2SiCl2 with K[C5H4tBu], Li[C5H4SiMe3] or K[C5H3tBuMe-3] followed by treatment with K[C5H4CH2CH2NMe2] yields mixed substituted dicyclopentadienyldimethylsilanes which after double deprotonation with KH afford the dipotassium salts K2[Me2Si(C5H3tBu-3)(C5H3CH2CH2NMe2-3)] ( 1 ), K2[Me2Si · (C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)] ( 2 ), and K2[Me2Si · (C5H2tBu-3-Me-5)(C5H3CH2CH2NMe2-3)] ( 3 ), respectively. The reaction of 1 , 2 , or 3 with LnCl3(THF)x (Ln = Y, La, Nd, Sm, Er, Lu) leads to the complexes [Me2Si(C5H3tBu-3) · (C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 4 a ), Sm ( 4 c ), Lu ( 4 e )], [Me2Si(C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 5 a ), Sm ( 5 c ), Lu ( 5 e )], and [Me2Si(C5H2tBu-3-Me-5)(C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 6 a ), Nd ( 6 b ), Sm ( 6 c ), Er ( 6 d ), Lu ( 6 e )], respectively. Alkylation of 4 a , 4 c , 5 a , and 6 b , 6 e with LiCH3, LiCH2SiMe3, and LiCH(SiMe3)2 produces the alkylmetallocenes [Me2Si(C5H3tBu-3) · (C5H3CH2CH2NMe2-3)]LnR [R = CH3, Ln = Y ( 7 a ), Sm ( 7 c ); R = CH2SiMe3, Ln = Y ( 8 a )], [Me2Si(C5H3SiMe3-3) · (C5H3CH2CH2NMe2-3)]YCH3 ( 9 a ), and [Me2Si(C5H2tBu3-Me-5)(C5H3CH2CH2NMe2-3)]LnR (R = CH3, Ln = Lu ( 10 e ); R = CH2SiMe3, Ln = Lu ( 11 e ); R = CH(SiMe3)2, Ln = Nd ( 12 b ), Lu ( 12 e )], respectively. All new compounds were characterized by elemental analyses, NMR spectroscopy and mass spectrometry. The molecular structure of 6 c and 6 e was determined by single crystal X-ray structure analysis. 相似文献
17.
The Reaction Behaviour of Lithiated Aminosilanes RR′Si(H)N(Li)SiMe3 The bis(trimethylsilyl)aminosubstituted silances RR′Si(H)N(SiMe3)2 11 – 16 (R,R′ = Me, Me3SiNH, (Me3Si)2N) are obtained by the reaction of the lithium silylamides RR′Si(H)N(Li)SiMe3 1 – 10 (R,R′ = Me3SiNLi, Me, Me3SiNH, (M3Si)2N) with chlorotrimethylsilane in the polar solvent tetrahydrofurane (THF). In the reaction of the lithium silylamides [(Me3Si)2N]2(Me3SiNLi)SiH 10 with chlorotrimethylsilane in THF the rearranged product 1,1,3-tris[bis(trimethylsilyl)amino]-3-methyl-1,3-disila-butane [(Me3Si)2N]2Si(H)CH2SiMe2N(SiMe3)2 17 is formed. The reaction of the lithium silyamides RR′ Si(H)N(Li)SiMe3 1 – 3 (1: R = R′ = Me; 2: R = Me, R′ = Me3SiNH; 3: R = Me, R′ = Me3SiNLi) with chlorotrimethylsilane in the nonpolar solvent n-hexane gives the cyclodisilazanes [RR′ Si? NSiMe3]2 18 – 22 (R = Me, Me3SiNH, (Me3Si)2N; R′ = Me, Me3SiNH, (Me3Si)2N, N(SiMe3)Si · Me(NHSiMe3)2) and trimethylsilane. The lithium silylamides 4 , 5 , 6 , 9 , 10 (4: R = R′ = Me3SiNH; 5: R = Me3SiNH, R′ = Me3SiNLi; 6: R = R′ = Me3SiNLi; 9: R = (Me3Si)2N, R ′ = Me3SiNLi; 10: R = R′ = (Me3Si)2N) shows with chlorotrimethylsilane in n-hexane no reaction. The crystal structure of 17 and 21 are reported. 相似文献
18.
Abinet E Martin D Standfuss S Kulinna H Spaniol TP Okuda J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):15014-15026
The preparation and characterization of a series of neutral rare‐earth metal complexes [Ln(Me3TACD)(η3‐C3H5)2] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane anion (Me3TACD?) are reported. Upon treatment of the neutral allyl complexes [Ln(Me3TACD)(η3‐C3H5)2] with Brønsted acids, monocationic allyl complexes [Ln(Me3TACD)(η3‐C3H5)(thf)2][B(C6X5)4] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me3TACD)H2]n (Ln=Y, n=3; La, n=4; Sm). X‐ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me3TACD)R2]n (R=η3‐C3H5, n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring‐opening conditions. 相似文献
19.
On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions
Kevin Bläsing Dr. Rene Labbow Dr. Dirk Michalik Dr. Fabian Reiß Prof. Dr. Axel Schulz Dr. Alexander Villinger Svenja Walker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1640-1652
Attempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3Si)3E]+ (E=O, S), by reacting [Me3Si-H-SiMe3][B(C6F5)4] and Me3Si[CB] (CB−=carborate=[CHB11H5Cl6]−, [CHB11Cl11]−) with Me3Si-E-SiMe3. In the reaction of Me3Si-O-SiMe3 with [Me3Si-H-SiMe3][B(C6F5)4], a ligand exchange was observed in the [Me3Si-H-SiMe3]+ cation leading to the surprising formation of the persilylated [(Me3Si)2(Me2(H)Si)O]+ oxonium ion in a formal [Me2(H)Si]+ instead of the desired [Me3Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3Si)3S]+ ion was formed and isolated as [B(C6F5)4]− and [CB]− salt, when Me3Si-S-SiMe3 was treated with either [Me3Si-H-SiMe3][B(C6F5)4] or Me3Si[CB]. However, the addition of Me3Si[CB] to Me3Si-O-SiMe3 unexpectedly led to the release of Me4Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3Si-μO-SiMe2]2[CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3Si)3E]+ and [(Me3Si)2(Me2(H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3Si)3E]+ ion into a cyclic dichalconium dication [Me3Si-μE-SiMe2]22+. 相似文献
20.
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 相似文献