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1.
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   

2.
The reactions of dilithium salt of trans-1,2-bis(trimethylsilylamino)cyclohexane with anhydrous lanthanide trichlorides LnCl3 (Ln = Yb, Nd) in THF afforded the dianionic binuclear tricycles of lanthanide chlorides {Li(THF)3[LnCl(μ2-trans-1,2-(NSiMe3)2C6H10)(μ2-Cl)]}2·2THF (Ln=Yb 1, Nd 2) in moderate yields. Both of the bridged complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that the two complexes are the analogues which have a tricyclic framework built by two bridged lanthanide metals, four nitrogens and four carbons from two diamide ligands. Each lanthanide metal coordinates to three nitrogen atoms and two chlorines to form a distorted trigonal bipyramid and connects with a lithium by a bridging chlorine.  相似文献   

3.
Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)6(ClO4)3. 2H2O (Ln=La, Sm, Dy and Ho); Ln(CyPO)7 (ClO4)3. 2H2O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)5 (ClO4)3. 2H2O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)6 (ClO4)3 (Ln=La, Pr, Nd and Ho); and Ln (CpicO)5 (ClO4)3 (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)6 (ClO4)3 (Ln=La and Nd); Ln(DMPicO)7 (ClO4)3 (Ln=Gd, Er and Yb); and Ln(DMPicO)8 (ClO4)3 (Ln=Dy and Ho).  相似文献   

4.
Preparation and Structure of Tris[2,4,6-tris(trifluormethyl)thiophenolato]indium (III) Etherate Reaction of sodium [2,4,6-tris(trifluoromethyl)thiophenolate and InCl3 in the molar ratio of 1:3 in diethylether forms tris 2,4,6-tris(trifluoromethyl)thiophenolato]indium(III) etherate 1 in 92% yield. 1 was also obtained by reaction of CpIn (Cp = C5H5) and C6H2(CF3)3SH. The structure of 1 is discussed.  相似文献   

5.
齐民华  沈琪等 《中国化学》2002,20(6):564-569
The reaction between K(1‐C5H9C9H6) and anhydrous LnCl3 (Ln=Sm, Yb) in the molar ratio of 2:1 in THF with subsequent treatment by Na‐K alloy afforded (1‐C5H9C9H6)2Ln‐(THF)n(Ln=Sm, n=1; Ln=Yb, n=2), while the reaction of Sml2 with K(1‐C5H9C9H6) in the molar ratio of 1:2 in THF gave the anionic complex K(1‐C5H9C9H6)3Sm(THF)3. The X‐ray structure of (1‐C5H9C9H6)2Yb(THF)2 showed that central metal Yb is coordinated by two cyclopentadienyl rings of 1‐cyclopentylindenyls and two oxygen atoms from two tetrahydrofuran molecules to form pseudo‐tetrahedral coordinate geometry. All these complexes are active for the polymerization of acrylonitrile.  相似文献   

6.
Treatment of Ln(NO3)3?nH2O with 1 or 2 equiv 2,2′‐bipyrimidine (BPM) in dry THF readily afforded the monometallic complexes [Ln(NO3)3(bpm)2] (Ln=Eu, Gd, Dy, Tm) or [Ln(NO3)3(bpm)2]?THF (Ln=Eu, Tb, Er, Yb) after recrystallization from MeOH or THF, respectively. Reactions with nitrate salts of the larger lanthanide ions (Ln=Ce, Nd, Sm) yielded one of two distinct monometallic complexes, depending on the recrystallization solvent: [Ln(NO3)3(bpm)2]?THF (Ln=Nd, Sm) from THF, or [Ln(NO3)3(bpm)(MeOH)2]?MeOH (Ln=Ce, Nd, Sm) from MeOH. Treatment of UO2(NO3)2?6H2O with 1 equiv BPM in THF afforded the monoadduct [UO2(NO3)2(bpm)] after recrystallization from MeOH. The complexes were characterized by their crystal structure. Solid‐state luminescence measurements on these monometallic complexes showed that BPM is an efficient sensitizer of the luminescence of both the lanthanide and the uranyl ions emitting visible light, as well as of the YbIII ion emitting in the near‐IR. For Tb, Dy, Eu, and Yb complexes, energy transfer was quite efficient, resulting in quantum yields of 80.0, 5.1, 70.0, and 0.8 %, respectively. All these complexes in the solid state were stable in air.  相似文献   

7.
Recrystallization of Ln(NO3)3 (Ln = Sm, Eu, Yb) in the presence of 18‐crown‐6 under aqueous conditions yielded [Ln(NO3)3(H2O)3] · 18‐crown‐6. X‐ray crystallography revealed isomorphous structures for each of the lanthanide complexes where [Ln(NO3)3(H2O)3] is involved in hydrogen bonding interactions with 18‐crown‐6. The transition point where the structural motif changes from [Ln(18‐crown‐6)(NO3)3] (with the metal residing in the crown cavity) to [Ln(NO3)3(H2O)3] · 18‐crown‐6 has been identified as at the Nd/Sm interface. A similar investigation involving [Ln(tos)3(H2O)6] (tos = p‐toluenesulfonate) and 18‐crown‐6 were resistant to crown incorporation. X‐ray studies show extensive intra‐ and intermolecular hydrogen bonding is present.  相似文献   

8.
New Syntheses and Crystal Structures of Bis(fluorophenyl) Mercury, Hg(Rf)2 (Rf = C6F5, 2, 3, 4, 6‐F4C6H, 2, 3, 5, 6‐F4C6H, 2, 4, 6‐F3C6H2, 2, 6‐F2C6H3) Bis(fluorophenyl) mercury compounds, Hg(Rf)2 (Rf = C6F5, C6HF4, C6H2F3, C6H3F2), are prepared in good yields by the reactions of HgF2 with Me3SiRf. The crystal structures of Hg(2, 3, 4, 6‐F4C6H)2 (monoclinic, P21/n), Hg(2, 3, 5, 6‐F4C6H)2 (monoclinic, C2/m), Hg(2, 4, 6‐F3C6H2)2 (monoclinic, P21/c) and Hg(2, 6‐F2C6H3)2 (triclinic, P1) are described.  相似文献   

9.
Two types of sandwich complexes (η5‐MeOCH2CH2C9H6) Ln (η8‐C8H8) (THF)n [Ln=La (1), Nd(2), n=0; Sm(3), Dy (4) and Er (5). n = l] and (η5‐C4H7OCH2C9H6)Ln(η8‐C8H8) (THF) [Ln = La (6), Nd(7). Sm(8). Dy (9) and Er (10)] were synthesized by the reactions of LnCl3 with equivalent mole of K2C8H8, followed by treatment with corresponding potassium salt of ether‐substituted indenide. The molecular structures of 3 and 8 were determined by single crystal X‐ray diffraction. (η5 ‐MeOCH2CH2C9H6) Sm (η8‐C8H8) (THF) (3) monoclinic. Pt1/c, a = 1.4793(3) nm, b = 0.8716 (2) nm, c = 1.6149 (3) nm, β = 98. 17(3), V = 2.0612(7) nm3, Z = 4, R(F)=0.0362. (η5‐C4H7OCH2C9H6)Sm(η8‐C8H8)(THF) (8) orthorhombic. p212121. a = 0.8754(2) nm, b = 1.1000(2) nm, c = 2.3117 (5) nm, V = 2.2260(8) nm3, Z=4, R(F) =0.0497.  相似文献   

10.
《Polyhedron》1988,7(1):79-81
The air and moisture stable complexes [Ln{HB(C3N2H3)3}2{MeC(O)CHC(O)Me}] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Yb, Lu, Y), have been prepared and characterized. The molecular structures of the compounds with Ln = Ce and Yb reveal that a substantial distortion of the coordination geometry found for Ce3+ is necessary to allow the ligand set to accommodate the smaller Yb3+ ion.  相似文献   

11.
Reaction of LnCl3 first with three equivalent of C5H5Na in THF, then with one equivalent of N‐phenyldiethanolamine in THF‐DME afforded complexes of {[(C5H5)Ln((‐OCH2CH2)2N(C6H5)]4((4‐Cl)}[Na(DME)4] (Ln=Sm ( 1 ), Yb ( 2 )), being characterized by infrared spectra, elemental analyses and X‐ray crystallography. They are ionic pair compounds. The anionic part is a cluster, which can be viewed as a cyclic tetramer with four (C5H5)Ln units bridged by four pairs of OR groups, forming a pinwheel structure. Both the complexes can catalyze the ring‐opening polymerization of ε‐caprolactone under mild conditions, and complex 1 is more active than complex 2 . The polymerization accords with one order reaction kinetics for monomer concentration. The molecular weight increases with the yield increasing, and the molecular weight distribution is rather narrow (1.19相似文献   

12.
于晓燕  金国新  翁林红 《中国化学》2002,20(11):1256-1262
IntroductionUptodateconsiderableattentionhasbeendevotedtothemetalcomplexeswithchalcogenolateligands .1,2Recentlytransitionmetalcomplexescontainingachelating1,2 dicarba closo dodecabarane 1,2 dichalcogenolatelig ands3 10 haveattractedagreatdealofinterestduetot…  相似文献   

13.
Interaction of a series of lanthanide cations (Ln3+) with a symmetrical octamethyl-substituted cucurbituril (OMeQ[6]) has been investigated. X-ray single-crystal diffraction analysis has revealed that the interaction results in the formation of adducts of OMeQ[6] with aqua complexes of lanthanide cations ([Ln(H2O)8]3+), Ln = Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb in OMeQ[6]–Ln(NO3)3–H2O systems. However, no solid crystals were obtained from systems containing La, Ce, Pr, Nd and Sm. X-ray diffraction analysis has revealed that although the solid adducts fall into two isomorphous groups, there are no significant differences in the interactions between OMeQ[6] and [Ln(H2O)8]3+ complexes and in the corresponding supramolecular assemblies. Thermodynamic parameters for the interaction between OMeQ[6] and [Ln(H2O)8]3+ complexes based on isothermal titration calorimetry experiments show two periods corresponding to the above two systems, with the lighter lanthanide cations preferring to remain in solution and the heavier lanthanide cations forming crystalline solids. Electron spectroscopy has shown that interaction of OMeQ[6] with lanthanide cations could provide a means of isolating heavier lanthanide cations from their lighter counterparts.  相似文献   

14.
The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH2C(Me)N(2‐HO‐5‐But‐C6H3) (LH2, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe3)2(THF)]2 [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH2 with Ln[N(SiMe3)2]3(µ‐Cl)Li(THF)3 in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and 1H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

15.
Treatment of the chlorides (L2,6‐iPr2Ph)2LnCl (L2,6‐iPr2Ph = [(2,6‐iPr2C6H3)NC(Me)CHC(Me)N(C6H5)]?) with 1 equiv. of NaNH(2,6‐iPr2C6H3) afforded the monoamides (L2,6‐iPr2Ph)2LnNH(2,6‐iPr2C6H3) (Ln = Y ( 1 ), Yb ( 2 )) in good yields. Anhydrous LnCl3 reacted with 2 equiv. of NaL2,6‐iPr2Ph in THF, followed by treatment with 1 equiv. of NaNH(2,6‐iPr2C6H3), giving the analogues (L2,6‐iPr2Ph)2LnNH(2,6‐iPr2C6H3) (Ln = Sm ( 3 ), Nd ( 4 )). Two monoamido complexes stabilized by two L2‐Me ligands, (L2‐Me)2LnNH(2,6‐iPr2C6H3) (L2‐Me = [N(2‐MeC6H4)C(Me)]2CH)?; Ln = Y ( 5 ), Yb ( 6 )), were also synthesized by the latter route. Complexes 1 , 2 , 3 , 4 , 5 , 6 were fully characterized, including X‐ray crystal structure analyses. Complexes 1 , 2 , 3 , 4 , 5 , 6 are isostructural. The central metal in each complex is ligated by two β‐diketiminato ligands and one amido group in a distorted trigonal bipyramid. All the complexes were found to be highly active in the ring‐opening polymerization of L‐lactide (L‐LA) and ε‐caprolactone (ε‐CL) to give polymers with relatively narrow molar mass distributions. The activity depends on both the central metal and the ligand (Yb < Y < Sm ≈ Nd and L2‐Me < L2,6‐iPr2Ph). Remarkably, the binary 3/benzyl alcohol (BnOH) system exhibited a striking ‘immortal’ nature and proved able to quantitatively convert 5000 equiv. of L‐LA with up to 100 equiv. of BnOH per metal initiator. All the resulting PLAs showed monomodal, narrow distributions (Mw/Mn = 1.06 ? 1.08), with molar mass (Mn) decreasing proportionally with an increasing amount of BnOH. The binary 4/BnOH system also exhibited an ‘immortal’ nature in the polymerization of ε‐CL in toluene. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

16.
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   

17.
Organometallic Compounds of the Lanthanides. 139 Mixed Sandwich Complexes of the 4 f Elements: Enantiomerically Pure Cyclooctatetraenyl Cyclopentadienyl Complexes of Samarium and Lutetium with Donor‐Functionalized Cyclopentadienyl Ligands The reactions of [K{(S)‐C5H4CH2CH(Me)OMe}], [K{(S)‐C5H4CH2CH(Me)NMe2}] and [K{(S)‐C5H4CH(Ph)CH2NMe2}] with the cyclooctatetraenyl lanthanide chlorides [(η8‐C8H8)Ln(μ‐Cl)(THF)]2 (Ln = Sm, Lu) yield the mixed cyclooctatetraenyl cyclopentadienyl lanthanide complexes [(η8‐C8H8)Sm{(S)‐η5 : η1‐C5H4CH2CH(Me)OMe}] ( 1 a ), [(η8‐C8H8)Ln{(S)‐η5 : η1‐C5H4CH2CH(Me)NMe2}] (Ln = Sm ( 2 a ), Lu ( 2 b )) and [(η8‐C8H8)Ln{(S)‐η5 : η1‐C5H4CH(Ph)CH2NMe2}] (Ln = Sm ( 3 a ), Lu ( 3 b )). For comparison, the achiral compounds [(η8‐C8H8)Ln{η5 : η1‐C5H4CH2CH2NMe2}] (Ln = Sm ( 4 a ), Lu ( 4 b )) are synthesized in an analogous manner. 1H‐, 13C‐NMR‐, and mass spectra of all new compounds as well as the X‐ray crystal structures of 3 b and 4 b are discussed.  相似文献   

18.
Searching for prospective luminescent materials, the series of new lanthanide coordination compounds CsLnL4 (Ln = La, Pr, Nd, Sm – Er, and Yb; L? = {C6H5CONPO(OCH3)2}-) was synthesized. X-ray diffraction studies of CsNdL4 and CsYbL4 have been performed establishing polymeric structures of the tetrakis-complexes built from [LnL4]? anions and cesium cations functioning as linkers. The IR, absorption, emission, excitation spectra, and decay time measurements at 298 and 77 K, as well as thermal gravimetric analyses, were used to characterize the complexes.  相似文献   

19.
As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt=C5H2tBu3-1,2,4, 1-Dy ) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] ( 1-Ln ) for all the heavier Ln from Gd–Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F51-F)B(C6F5)3}] ( 1-Ln ; La–Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] ( 2-Ln ) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] ( 1-Sm ) is isolated, which like heavier 1-Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1-Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.  相似文献   

20.
The multi-step dehydration and decomposition of trivalent lanthanum and lanthanide heptanediate polyhydrates were investigated by means of thermal analysis completed with infrared study. Further more, X-ray diffraction data for investigated heptanediate complexes of general stoichiometry Ln2(C7H10O4)3.nH2O (wheren=16 in the case of La, Ce, Pr, Nd and Sm pimelates,n=8 for Eu, Gd, Tb, Dy, Er and Tm pimelates,n=12 for Ho, Yb and Lu pimelates) were also reported.
Zusammenfassung Mittels TG, DTG, DTA wurde in Verbindung mit IR-Methoden der mehrstufige Dehydratations- und der Zersetzungsvorgang der Polyhydrate der PimelinsÄuresalze von dreiwertigem Lanthan und dreiwertigen Lanthanoiden untersucht. Röntgendiffraktionsdaten der untersuchten Heptandiat-Komplexe mit der allgemeinen Formel Ln2(C7H10O4)3 nH2O (mitn=16 für Ln=La, Ce, Pr, Nd und Sm,n=8 für Ln=Eu, Gd, Tb, Dy, Er und Tm sowien=12 für Ln=Ho, Yb und Lu) werden ebenfalls gegeben.
  相似文献   

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