首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2], and [(C5Me5)Gd(CH2C6H5)2(thf)] YBr3 reacts with potassium benzyl and [K(C5Me5)] in THF to give KBr and the monobenzyl compound [(C5Me5)2 · Y(CH2C6H5)(thf)] 1 . The analogous reaction with SmBr3 in THF leads to the polymeric product [(C5Me5)2Sm(CH2C6H5)2 ∞ K(thf)2] 2 , with GdBr3 to [(C5Me5)Gd(CH2C6H5)2(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:
  • Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
  • Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
  • Space group P21/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.
  相似文献   

2.
《Polyhedron》1987,6(5):1143-1145
The complexes M(OR)2(thf)3 (M = Yb or Eu, R = 2,6-But2-4-MeC6H2; M = Yb, R = 2,4,6-But3C6H2 or 2,6-But2C6H3; thf = tetrahydrofuran) and M(NR2)2(thf)4 (M = Yb or Eu, R2N = carbazol-9-yl; M = Yb, R2N = 2-phenylindol-1-yl) have been prepared by reactions of (C6F5)2M (M = Yb or Eu) with substituted phenols, carbazole, or 2-phenylindole.  相似文献   

3.
On the Reaction of Dilithiumbiphenyl with SmBr3. The Crystal Structure of [(C24H16)SmBr(thf)2]2 · [C24H14] In THF SmBr3 forms with [(biph)Li2] the dimeric complex [(quaph)SmBr(thf)2]2 · [C24H14]. The structure was characterized by X-ray single crystal structure analysis (space group P1 (No. 2), Z = 1, a = 943.3(6) pm, b = 1 350.3(1) pm, c = 1 599.9(9) pm, α = 64.99(5)°, β = 89.02(5)°, γ = 73.02(6)°). The Sm iones are bridged by two Br iones. Coordination by one quaph and THF ligands leads to distorded octahedra coordination of the Sm iones. Additionally crystallizes one molecule dibenzonaphthacene.  相似文献   

4.
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   

5.
New reactive, divalent lanthanoid formamidinates [Yb(Form)2(thf)2] (Form=[RNCHNR]; R=o‐MeC6H4 (o‐TolForm; 1 ), 2,6‐Me2C6H3 (XylForm; 2 ), 2,4,6‐Me3C6H2 (MesForm; 3 ), 2,6‐Et2C6H3 (EtForm; 4 ), o‐PhC6H4 (o‐PhPhForm; 5 ), 2,6‐iPr2C6H3 (DippForm; 6 ), o‐HC6F4 (TFForm; 7 )) and [Eu(DippForm)2(thf)2] ( 8 ) have been prepared by redox transmetallation/protolysis reactions between an excess of a lanthanoid metal, Hg(C6F5)2 and the corresponding formamidine (HForm). X‐ray crystal structures of 2 – 6 and 8 show them to be monomeric with six‐coordinate lanthanoid atoms, chelating N,N′‐Form ligands and cis‐thf donors. However, [Yb(TFForm)2(thf)2] ( 7 ) crystallizes from THF as [Yb(TFForm)2(thf)3] ( 7 a ), in which ytterbium is seven coordinate and the thf ligands are “pseudo‐meridional”. Representative complexes undergo C? X (X=F, Cl, Br) activation reactions with perfluorodecalin, hexachloroethane or 1,2‐dichloroethane, and 1‐bromo‐2,3,4,5‐tetrafluorobenzene, giving [Yb(EtForm)2F]2 ( 9) , [Yb(o‐PhPhForm)2F]2 ( 10) , [Yb(o‐PhPhForm)2Cl(thf)2] ( 11) , [Yb(DippForm)2Cl(thf)] ( 12) and [Yb(DippForm)2Br(thf)] ( 16) . X‐ray crystallography has shown 9 to be a six‐coordinate, fluoride‐bridged dimer, 12 and 16 to be six‐coordinate monomers with the halide and thf ligands cis to each other, and 11 to have a seven‐coordinate Yb atom with “pseudo‐meridional” unidentate ligands and thf donors cis to each other. The analogous terbium compound [Tb(DippForm)2Cl(thf)2] ( 13 ), prepared by metathesis, has a similar structure to 11 . C? Br activation also accompanies the redox transmetallation/protolysis reactions between La, Nd or Yb metals, Hg(2‐BrC6F4)2, and HDippForm, yielding [Ln(DippForm)2Br(thf)] complexes (Ln=La ( 14 ), Nd ( 15 ), Yb ( 16 )).  相似文献   

6.
New Complexes of the Lanthanoides with Bidentate Ligands. The Crystal Structures of [(C17H17N2)GdBr2(thf)2] and [(C17H17N2)3Ln] (L = Sm, Gd) Reaction of [(AIP)Li] with GdBr3 leads to a new mononuclear complex [(AIP)GdBr2(thf)2] 1 . In contrast to this with SmI2 the compound [(AIP)3Sm] 2 is build up. Such complexes are also formed with Gd(OR*)3 (R* = OtBu2C6H3) and [(AIP)Li] in a 1:3 ratio, [(AIP)3Gd] 3 . The structures of 1–3 were characterized by X-ray single crystal structure analysis ( 1 : space group Pna21 (No. 33), Z = 4, a = 1 972.7(9) pm, b = 984.7(5) pm, c = 1 425.0(8) pm, α = β = γ = 90°; 2 · 2 THF: space group C2/c (No. 15), Z = 8, a = 3 644.4(9) pm, b = 1 437.5(5) pm, c = 2 334.4(7) pm, β = 1 21.07(6)°; 3 : space group P2(1)/c (No. 14), Z = 4, a = 1 872.9(1) pm, b = 1 064.6(1) pm, c = 2 282.4(2) pm, β = 103.75(8)°).  相似文献   

7.
Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd2(acac)2(oxam)]) reacted with Li–C≡C–C6H5 in THF with formation of [Pd(C≡C–C6H5)4Li2(thf)4] ( 1a ). Reaction of [Pd2(acac)2(oxam)] with a mixture of 6 equiv. Li–C≡C–C6H5 and 2 equiv. LiCH3 resulted in the formation of [Pd(CH3)(C≡C–C6H5)3Li2(thf)4] ( 2 ), and the dimeric complex [Pd2(CH3)4(C≡C–C6H5)4Li4(thf)6] ( 3 ) was isolated upon reaction of [Pd2(acac)2(oxam)] with a mixture of 4 equiv. Li–C≡C–C6H5 and 4 equiv. LiCH3. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, 1H‐, 13C‐, 7Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh3)4 in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C6H5)2(PPh3)2] and [Pd(η2‐O2)(PPh3)2]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction.  相似文献   

8.
The reaction of MCl4(thf)2 (M = Zr, Hf) with 1,4-dilitiobutane in diethyl ether at –25 °C or at 0 °C with a molar ratio of 1 : 3 yields the homoleptic “ate” complexes [(thf)4Li] [{(thf)Li}M(C4H8)3] 1 - Zr (M = Zr) and 1 - Hf (M = Hf). The crystalline compounds form ion lattices with solvent-separated [(thf)4Li]+ cations and [{(thf)Li}M(C4H8)3] anions. The NMR spectra at –20 °C show magnetic equivalence of the M–CH2 and of the β-CH2 groups of the butane-1,4-diide ligands on the NMR time scale. Analogous reactions of MCl4(thf)2 with 1,4-dilithiobutane with a molar ratio of 1 : 2 proceed unclear. However, single crystals of [Li(thf)4] [HfCl5(thf)] ( 2 ) can be isolated with the hafnium atom in a distorted octahedral coordination sphere of five chloro and one thf ligand. NMR spectra allow to elucidate the time-dependent degradation of 1-Hf and 1-Zr in THF and toluene at 25 °C via THF cleavage. Addition of tmeda to a solution of 1-Zr allows the isolation of intermediately formed [{(tmeda)Li}2Zr(nBu)2(C4H8)2] ( 3 ).  相似文献   

9.
The lanthanidocene complex [Sm(BH4)(C12H19)2(C4H8O)], (I), shows a distorted tetrahedral arrangement around the central SmIII atom. It consists of two η5‐isopropyltetramethylcyclopentadienyl ligands, one tetrahydroborato (BH4?) ligand bridging via H atoms to the lanthanide atom and one coordinating tetrahydrofuran (thf) molecule. The BH4? unit of (I) coordinates as a tridentate ligand with three bridging H atoms and one terminal H atom [Sm—B—H4 176 (2)°]. The η5‐isopropyl­tetra­methylcyclopentadienyl ligands of this bent‐sandwich complex [Cp1—Sm—Cp2 133.53 (1)° where Cp denotes the centroid of the cyclopentadienyl ring] adopt staggered conformations.  相似文献   

10.
Monocationic bis‐allyl complexes [Ln(η3‐C3H5)2(thf)3]+[B(C6X5)4]? (Ln=Y, La, Nd; X=H, F) and dicationic mono‐allyl complexes of yttrium and the early lanthanides [Ln(η3‐C3H5)(thf)6]2+[BPh4]2? (Ln=La, Nd) were prepared by protonolysis of the tris‐allyl complexes [Ln(η3‐C3H5)3(diox)] (Ln=Y, La, Ce, Pr, Nd, Sm; diox=1,4‐dioxane) isolated as a 1,4‐dioxane‐bridged dimer (Ln=Ce) or THF adducts [Ln(η3‐C3H5)3(thf)2] (Ln=Ce, Pr). Allyl abstraction from the neutral tris‐allyl complex by a Lewis acid, ER3 (Al(CH2SiMe3)3, BPh3) gave the ion pair [Ln(η3‐C3H5)2(thf)3]+[ER31‐CH2CH?CH2)]? (Ln=Y, La; ER3=Al(CH2SiMe3)3, BPh3). Benzophenone inserts into the La? Callyl bond of [La(η3‐C3H5)2(thf)3]+[BPh4]? to form the alkoxy complex [La{OCPh2(CH2CH?CH2)}2(thf)3]+[BPh4]?. The monocationic half‐sandwich complexes [Ln(η5‐C5Me4SiMe3)(η3‐C3H5)(thf)2]+[B(C6X5)4]? (Ln=Y, La; X=H, F) were synthesized from the neutral precursors [Ln(η5‐C5Me4SiMe3)(η3‐C3H5)2(thf)] by protonolysis. For 1,3‐butadiene polymerization catalysis, the yttrium‐based systems were more active than the corresponding lanthanum or neodymium homologues, giving polybutadiene with approximately 90 % 1,4‐cis stereoselectivity.  相似文献   

11.
Arylvanadium (III) Compounds. VI. Preparation and Properties of Lithium Trimesityl organyl Vanadates Trimesityl vanadium reacts with LiR (R = Ph, o-Tol, Dmop, CH3, CPh3) forming complexes Li(thf)4 VMes3R. With Li2C6H4 and Li2C2 the compounds Li2(thf) 8 V(μ-C6H4)Mes6 and Li2(thf)8V(μ-C2)Mes6 are obtained. All compounds are characterized by their thermal, magnetical, and spectral properties.  相似文献   

12.
The homocycles (RBi)n (n = 3–5) react with MeC5 H4Mn(CO)2(thf) (thf = tetrahydrofuran) or Fe2(CO)9 to give Bi2[Mn(CO)2MeC5 H4]3 (1) or Bi2Fe3(CO)9 (3). Reaction of R4Bi2 (R = Me3SiCH2) with Fe2(CO)9 in toluene gives R2Bi2Fe2(CO)8 (4) and R4Bi2Fe(CO)4 (5). The heterocycles (RBiS)2(R = 2-(Me2NCH2)C6 H4 (6), 2, 6-(Me2NCH2)2 C6 H4 (7) are formed by reaction of the corresponding dihalides RBiCl2 with Na2S. The reaction of (RBiS)2(R = 2-(Me2NCH2)C6 H4) with W(CO)5(thf) leads to (RBiS)2[W(CO)5]2 (8).  相似文献   

13.
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   

14.
The thermal decomposition of the complex Ni(CN)(C6H5)(PCy3)2 (Cy = cyclohexyl) in decalin has been examined. The complex reacts with P(OC2H5)3 to give C6H5CN in quantitative yield. The mechanism of this reaction has been investigated and compared with that of the similar reaction shown by Ni(CN)(C6H5)(PEt3)2. The results indicate that the easiest path for the reaction involves a bimolecular attack of P(OC2H5)3 at the metal atom before reductive elimination of C6H5CN.  相似文献   

15.
The acid–base reaction between Y(CH2SiMe3)3(thf)2 and the pyridyl‐functionalized cyclopentadienyl (Cp) ligand C5Me4H? C5H4N (1 equiv) at 0 °C afforded a mixture of two products: (η5:κ‐C5Me4? C5H4N)Y(CH2SiMe3)2(thf) ( 1 a ) and (η5:κ‐C5Me4? C5H4N)2YCH2SiMe3 ( 1 b ), in a 5:2 ratio. Addition of the same ligand (2 equiv) to Y(CH2SiMe3)3(thf)2, however, generated 1 b together with the novel complex 1 c , the first well defined yttrium mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)[C5HMe33‐CH2)‐C5H4N‐κ]Y(CH2SiMe3) containing a rare κ/η3‐allylic coordination mode in which the C? H bond activation occurs unexpectedly with the allylic methyl group rather than conventionally on Cp ring. If the central metal was changed to lutetium, the equimolar reaction between Lu(CH2SiMe3)3(thf)2 and C5Me4H? C5H4N exclusively afforded the bis(alkyl) product (η5:κ‐C5Me4? C5H4N)Lu(CH2SiMe3)2(thf) ( 2 a ). Similarly, the reaction between the ligand (2 equiv) and Lu(CH2SiMe3)3(thf)2 gave the mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)2LuCH2SiMe3 ( 2 b ), in which no ligand redistribution was observed. Strikingly, treatment of Sc(CH2SiMe3)3(thf)2 with C5Me4H? C5H4N in either 1:1 or 1:2 ratio at 0 °C generated the first cyclopentadienide‐based scandium zwitterionic “tuck‐over” complex 3 , (η5:κ‐C5Me4? C5H4N)Sc(thf)[μ‐η51:κ‐C5Me3(CH2)‐C5H4N]Sc(CH2SiMe3)3. In the zwitterion, the dianionic ligand [C5Me3(CH2)‐C5H4N]2? binds both to Sc13+ and to Sc23+, in η5 and η1/κ modes. In addition, the reaction chemistry, the molecular structures, and the mechanism are also discussed in detail.  相似文献   

16.
(C5H5)2Pb reacts with HX to give (C5H5)PbX or PbX2, X = Cl,Br,CH3CO2, with BF3·Et2O to give (C5H5)2PbBF3 and with TCNE to give (C5H5)2Pb·O·5TCNE or (C5H5)2Pb·TCNE.  相似文献   

17.
Synthesis of Mesityl Aluminium Compounds Trimesityl aluminium, Al(C9H11)3(thf), is easily prepared from aluminium chloride and solutions of Mg(C9H11)Br or Mg(C9H11)2 in tetrahydrofuran. It loses tetrahydrofuran forming quite stable Al(C9H11)3. Al(C9H11)Cl2(thf) and Al(C9H11)Cl(thf) are obtained, too, from AlCl3 and Al(C9H11)3 or Mg(C9H11)2, respectively.  相似文献   

18.
The complexes (C5H5)2M[P(OCH3)3]2 (M = Ti and Zr) can be prepared by condensing sodium atoms at ?100°C into tetrahydrofuran solutions containing (C5H5)2MCl2 and excess trimethyl phosphite.  相似文献   

19.
Reaction of LnCl3(thf) x (Ln = Y, La, Yb, Lu) with NaCpPhn (CpPhn = 1,3-Ph2C5H3, 1,2,4-Ph3C5H2, Ph4C5H) leads to formation of monocyclopentadienyl dichloride complexes Yb(Ph2C5H3)Cl2(thf)3 (1), Ln(Ph3C5H2)Cl2(thf)3 (Ln = Y (2), Lu (3)), La(Ph4C5H)Cl2(thf)3 (4). Molecular structures of 1, 2 and the polynuclear complex [(Ph3C5H2)3Lu4(Cl)7(O)(thf)3] (5), which is a partial hydrolysis product of 3, have been established by the X-ray method.  相似文献   

20.
Summary Equimolar quantities of [MI2(CO)3(NCMe)2] (M = Mo or W) and C3H4N2 (pyrazole) react in CH2C12 at room temperature to give the iodo-bridged dimers [M(μ-I) (CO)3(C3H4N2)]2 (1) and (2). Two equivalents of C3H4N2 react with [MI2(CO)3(NCMe)2] (M = Mo or W) to give the bis(pyrazole) complexes [MI2(CO)3(C3H4N2)2] (3) and (4) in good yield. Three and four equivalents of pyrazole react with [MoI2(CO)3(NCMe)2] to give the cationic complexes [MoI(CO)3(C3H4N2)3]I (5) and [MoI(CO)2(C3H4N2)4]I (6), respectively. The mixed ligand complexes [MI2(CO)3(C3H4N2)L] (M = Mo or W; L = PPh3, AsPh3 or SbPh3) (7)-(12) are prepared by reacting equimolar amounts of [MI2(CO)3(NCMe)2] and L in CH2C12 at room temperature, followed by an in situ reaction with one equivalent of C3H4N2. The MoSnCl3 complex [MoCl(SnCl3)(CO)3(C3H4N2)2] (13) is prepared in an analogous manner using acetone as the solvent, whilst the mixed ligand compound [MoCl(SnQ3)(CO) 3(C3H4N2)(PPh3)] (14) was prepared by treating the dimeric complex [Mo(μ-Cl)(SnCl3)(CO)3(PPh3)]2 with two equivalents of C3H4N2. All the new complexes were characterised by elemental analysis (carbon, hydrogen and nitrogen), i.r. and 1H n.m.r. spectroscopy.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号