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 530 毫秒
1.
Ytterbium complexes, Cp2Yb(-2:2-DAB)Li(DME) (1) and CpYb(DAB)K(THF)2 (2), containing a bridging diazadiene ligand were prepared by the reaction of CpYbCl2(THF)3 with (DAB)Li2 (11) and (DAB)K+ (12) (DAB = But-N=CH-CH=N-But). The structure of complex1 was established by X-ray diffraction analysis. The complex is binuclear: the Yb atom of the Cp2Yb fragment and the Li atom, which is bonded as well with the chelating DME molecule, are linked by the DAB ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 148–151, January, 1994.  相似文献   

2.
Oxidation of (C5Me5)2Yb(THF)2 with diazabutadiene ButN=CHCH=NBut (DAD) afforded the (C5Me5)2Yb(ButNCHCHNBut) complex (1). The magnetic measurements and X-ray diffraction study confirmed the trivalent state of the ytterbium atom and the radical nature of the DAD ligand in complex 1. The oxidation state of ytterbium in the (C5Me5)2YbDAD—solvent system depends on the coordinating properties of the solvent, whereas the ytterbium atom in the Cp2YbDAD complex (2) remains trivalent regardless of the solvent nature. In complex 2, the redox replacement of DAD·– with 9-fluorenone accompanied by the pinacol dimerization of 9-fluorenone and detachment of one Cp ligand from the ytterbium atom gave rise to the dimeric [CpYb(2-OC13H8-C13H8O)(THF)]2 complex (3). The structure of complex 3 was established by X-ray diffraction analysis.  相似文献   

3.
The interaction of the ytterbium bis(indenyl) complex (C9H7)2YbII(THF)2 (1) with the 1,4-diazabutadiene 2-MeC6H4N=C(Me)-C(Me)=NC6H4Me-2 (MeDAD) is accompanied by the oxidation of the metal atom to the trivalent state and results in a paramagnetic compound of the metallocene type (C9H7)2YbIII(MeDAD−·) (3) containing the radical anion of 1,4-diazabutadiene. The structure of the complex 3 was determined by X-ray diffraction analysis. The reactions of the bis(indenyl) (1) and bis(fluorenyl) (C13H9)2YbII(THF)2 (2) derivatives of divalent ytterbium with the 1,4-diazabutadiene PhN=C(Ph)-C(Ph)=NPh (PhDAD) (with the molar ratio of the reactants 1:2) proceed with a complete cleavage of the bonds Yb-C and the oxidation of the ytterbium atom to the trivalent state and result in a homoligand complex (PhDAD−·)3Yb (6) containing three radical anion 1,4-diazadiene ligands. Complex 6 was also obtained by an exchange reaction of YbCl3 with PhDAD−·K+ (1: 3) in THF. Complex 6 was characterized by X-ray diffraction analysis.  相似文献   

4.
Polymeric (Cp2Yb·THF) n (1), ionicate-complex Cp3YbNa (2), and mono-adduct (But 2C5H3)2Yb·THF (3) were prepared through a reaction of CpNa (Cp = C5H5 or C5H3But 2) with Ybl2 in THF. Cooling complex (3) in THF at –100 °C gives a bis-adduct, which reversibly dissociates to give the mono-adduct, The (But 2C H , Yb·THF complex shows catalytic activity in the homogeneous hydrogenation of hex-l-ene and in the polymerization of styrene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No, 7, pp. 1833–1837, July, 1996.  相似文献   

5.
The stilbene complex of ytterbium (PhCH=CHPh)Yb(THF)2 (1) was prepared by the reaction of YbI2(THF)2 with a twofold excess of (PhCH=CHPh) Li+. Based on the data of IR and ESR spectroscopy and on the results of magnetic measurements, compound1 was characterized as a complex of divalent ytterbium with the stilbene dianion. The reactivity of complex1 toward different types of reagents was studied. The structure of the product of the reaction of1 with 2,4,6-tri(tert-butyl)phenol (2,4,6-But 3C6H2O)2Yb(THF)3 was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2345–2350, November, 1998.  相似文献   

6.
The reactions of ytterbium naphthalene complex C10H8Yb(THF)2 with 2-cyclopentadienylethanol, 1-cyclopentadienylpropan-2-ol, 3-cyclopentadienyl-1-butoxypropan-2-ol, and cyclopentadienyldimethylsilyl-tert-butylamine were studied. The bivalent ytterbium complexes with chelate bifunctional cyclopentadienyl ligands [(η5−C5H5)CH2CH21−O)]Yb(THF), [(η5−C5H5)CH2CH21−O)]Yb(DME). [(η5−C5H5)CH2CH(Me)(η1−O)]Yb(THF), [(η5−C5H5)CH2CH(CH2OC4H9)(η1−O)]Yb(THF), and [(η5−C5H5)SiMe21−N(Bu1))]Yb(THF) were obtained and characterized. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 742–745, April, 2000.  相似文献   

7.
Cp2YbCl(THF) crystallizes in the orthorhombic space group Pnma (Z = 4, a = 13.109(5), b = 11.851(4), c = 9.377(3) Å, R1 = 0.0412, wR2 = 0.0482), while Cp2YbBr(THF) is monoclinic (P21/n, Z = 4, a = 8.149(2), b = 12.997(2), c = 14.388(3) Å, β = 105.73(2)°, R1 = 0.0425, wR2 = 0.0436). The ligand arrangements around the formally eight coordinate Yb atoms are pseudo tetrahedral. These two determinations complete the first series of [Cp2LnX(L)] (X = F, Cl, Br, I) structures covering all halogens for one lanthanoid and cyclopentadienyl group.  相似文献   

8.
Reaction of Sml2(THF)2 with metallic lithium andtrans-stilbene in 1:2:2 ratio in DME gives the stilbene complex of divalent samarium (PhCHCHPh)Sm(DME)2. This complex reacts with hydrogen in THF to give SmH2(THF)2 and 1,2-diphenylethane. The reaction with (Me3Si)2NH gives the amide [(Me3Si)2N]2Sm(DME)2 and the reaction with triphenylgermane yields Ph3GeGePh3. Reaction of CpLuCl2(THF)2 with 2 equivalents of [PhCHCHPh]·Na+ in DME results in the dimerization of stilbene fragments to give anate-complex {Cp2Lu[μ-CH (Ph)CH(Ph)CH(Ph)CH(Ph)]}Na(DME)3. In the reaction of Cp2GdCl with [PhCHCHPh]·Na+, the known complex Cp3Gd(THF) was isolated as the only lanthanidecontaining product. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1442–1446, August, 2000.  相似文献   

9.
The reaction of the ytterbium(II) bis(indenyl) complex (C9H7)2Yb(thf)2 (1) with 2,2’-bipyridine afforded the diamagnetic (C9H7)2Yb(bipy) compound (2), whose structure was established by X-ray diffraction analysis. Under similar conditions, the reaction of complex 1 with 1,4-bis(2,6-diisopropylphenyl)-1,4-diazabuta-1,3-diene (DAD) led to oxidation of ytterbium giving rise to the paramagnetic (C9H7)2Yb(DAD) complex (3). Magnetic measurements, X-ray diffraction study, and 1H NMR spectroscopy in benzene confirmed the trivalent state of the ytterbium atom and the radical-anionic nature of the diazadiene ligand in complex 3. In the complex 3—solvent system, the oxidation state of metal depends on the coordination ability of the solvent. In benzene, complex 3 exists as (C9H7)2YbIII(DAD·-), whereas (C9H7)2YbII(thf)2 and DAD0 are present in THF.  相似文献   

10.
The equilibrium in the system water—electrolyte—cross-linked polymer containing immobilized 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene was studied. Immobilized calixarene 1 was shown to form 1∶1, 1∶2, 1∶3, and 1∶4 compounds with inorganic cations (Na+, Cs+, and NH4 +), and with organic cations (hexamethylen-tetramine and β-diethylaminoethylp-aminobenzoate) 1∶1 compounds are formed. The affinity of immobilized calixarene1 increases in the series of cations: hexamethylenetetramine <Na+, Cs+, NH4 +<β-diethylaminoethylp-aminobenzoate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2214–2216, November, 1998.  相似文献   

11.
The potassium dihydrotriazinide K(LPh,tBu) ( 1 ) was obtained by a metal exchange route from [Li(LPh,tBu)(THF)3] and KOtBu (LPh,tBu = [N{C(Ph)=N}2C(tBu)Ph]). Reaction of 1 with 1 or 0.5 equivalents of SmI2(thf)2 yielded the monosubstituted SmII complex [Sm(LPh,tBu)I(THF)4] ( 2 ) or the disubstituted [Sm(LPh,tBu)2(THF)2] ( 3 ), respectively. Attempted synthesis of a heteroleptic SmII amido‐alkyl complex by the reaction of 2 with KCH2Ph produced compound 3 due to ligand redistribution. The YbII bis(dihydrotriazinide) [Yb(LPh,tBu)2(THF)2] ( 4 ) was isolated from the 1:1 reaction of YbI2(THF)2 and 1 . Molecular structures of the crystalline compounds 2 , 3· 2C6H6 and 4· PhMe were determined by X‐ray crystallography.  相似文献   

12.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li] anion.  相似文献   

13.
Density functional theory was used to study gas-phase reactions between the Cp2*ZrMe+ cations, where Cp* = C5H5 (1), Me5Cp = C5Me5 (2), and Flu = C13H9 (3), and the ethylene molecule, Cp2*ZrMe+ + C2H4 → Cp2*ZrPr+ → Cp2*ZrAllyl+ + H2. The reactivity of the Cp2*ZrMe+ cations with respect to the ethylene molecule decreased in the series 1 > 32. Substitution in the Cp ring decreased the reactivity of the Cp2*ZrMe+ cations toward ethylene, in agreement with the experimental data on the comparative reactivities of complexes 1 and 3. The two main energy barriers along the reaction path (the formation of the C-C bond leading to the primary product Cp2*ZrPr+ and hydride shift leading to the secondary product Cp2*Zr(H2)Allyl+) vary in opposite directions in the series of the compounds studied. For Flu (3), these barriers are close to each other, and for the other compounds, the formation of the C-C bond requires the overcoming of a higher energy barrier. A comparison of the results obtained with the data on the activity of zirconocene catalysts in real catalytic systems for the polymerization of ethylene led us to conclude that the properties of the catalytic center changed drastically in the passage from the model reaction in the gas phase to real catalytic systems.  相似文献   

14.
The interaction of the Negishi reagent Cp2ZrBun 2 with 1,4-bis(tert-butyl)butadiyne ButC≡C-C≡CBut leads to four products: a five-membered zirconacyclocumulene complex Cp2Zr(η4-ButC4But) (2) synthesized earlier by another method, the previously unknown seven-membered zirconacyclocumulene Cp2Zr[η4-ButC4(But)-C(C2But)=CBut] (3) as well as small amounts of the zirconocene binuclear butatrienyl complex Cp2(Bun)Zr(ButC4But)Zr(Bun)Cp2 (4), and the dimeric acetylide [Cp2ZrC≡CBut]2 (5). The structure of complexes 2–5 was established by X-ray diffraction studies.  相似文献   

15.
CpCuPPh3 reacts with Pr, Er, Yb, Cp2Yb, and SmI2(THF)4 to form, in high yields, lanthanide cyclopentadienyl derivatives Cp2Yb, Cp3Ln (Ln = Pr, Er, Yb), and CpSmI2(THF)2. The initial agent CpCuPPh3 can be prepared in 95-98% yield by the reaction of t-BuOCu with CpH in the presence of PPh3.  相似文献   

16.
The synthesis of [TiInd(NCtBu2)Cl2] and the applications of [TiCp(NCtBu2)Cl2] (Cp=Ind, Cp*, Cp) as ethylene and propylene homopolymerisation catalysts, as well as its behaviour as catalysts of ethylene and 10-undecen-1-ol copolymerisation are described. The optimisation of the catalytic reactions showed that all compounds are very active homopolymerisation catalysts, particularly [TiInd(NCtBu2)Cl2] that gives 123.37 × 106 g/(molTi [E] h) and 50.77 × 106 g/(molTi [P] h) of linear polyethylene and atatic polypropylene, respectively. The less active homopolymerisation catalyst, [TiCp(NCtBu2)Cl2], is the most effective ethylene/10-undecen-1-ol copolymerisation catalyst, leading to the highest degree of polar monomer incorporation. The polymers obtained were characterised by NMR and DSC. The molecular structures of [TiCp(NCtBu2)Cl2] (Cp=Ind, Cp*) were determined by X-ray diffraction studies.  相似文献   

17.
Reduction of the bent-sandwich [·5-(Ph)Ind]2HfCl2 complex (1) (where (Ph) Ind is the 2-phenylindenyl anion) in a THF medium was studied by low-temperature cyclic voltammetry. Complex1 is stable in THF at a temperature lower than −50°C and undergoes reversible one-electron reduction to radical anion1 . −. Further one-electron reduction of1 . − to dianion1 2− is accompanied by the elimination of two Cl ions to form the bisindenyl sandwich [·5-(Ph)Ind]2Hf complex (2). This complex can undergo reversible one-electron reduction to the corresponding radical anion2 . −, which is stable within the cyclic voltammetry time scale. AtT=−30°C in a THF solution, complex1 was reduced to a diamagnetic (apparently, binuclear) HfIII complex, which was characterized by cyclic voltammetry. Synthesis and the crystal structure of complex1 are reported. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2161–2165, December, 1997.  相似文献   

18.
Reaction of bromoacylsilane 1 (pink solution) with tBu2MeSiLi (3.5 equiv) in a 4:1 hexane:THF solvent mixture at −78 °C to room temperature yields the solvent separated ion pair (SSIP) of silenyl lithium E‐[(tBuMe2Si)(tBu2MeSi)C=Si(SiMetBu2)] [Li⋅4THF]+ 2 a (green–blue solution). Removal of the solvent and addition of benzene converts 2 a into the corresponding contact ion pair (CIP) 2 b (violet–red solution) with two THF molecules bonded to the lithium atom. The 2 a ⇌ 2 b interconversion is reversible upon THF⇌ benzene solvent change. Both 2 a and 2 b were characterized by X‐ray crystallography, NMR and UV/Vis spectroscopy, and theoretical calculations. The degree of dissociation of the Si−Li bond has a large effect on the visible spectrum (and thus color) and on the silenylic 29Si NMR chemical shift, but a small effect on the molecular structure. This is the first report of the X‐ray molecular structure of both the SSIP and the CIP of any R2E=E′RM species (E=C, Si; E′=C, Si; M=metal).  相似文献   

19.
Reaction of bromoacylsilane 1 (pink solution) with tBu2MeSiLi (3.5 equiv) in a 4:1 hexane:THF solvent mixture at ?78 °C to room temperature yields the solvent separated ion pair (SSIP) of silenyl lithium E‐[(tBuMe2Si)(tBu2MeSi)C=Si(SiMetBu2)]? [Li?4THF]+ 2 a (green–blue solution). Removal of the solvent and addition of benzene converts 2 a into the corresponding contact ion pair (CIP) 2 b (violet–red solution) with two THF molecules bonded to the lithium atom. The 2 a ? 2 b interconversion is reversible upon THF? benzene solvent change. Both 2 a and 2 b were characterized by X‐ray crystallography, NMR and UV/Vis spectroscopy, and theoretical calculations. The degree of dissociation of the Si?Li bond has a large effect on the visible spectrum (and thus color) and on the silenylic 29Si NMR chemical shift, but a small effect on the molecular structure. This is the first report of the X‐ray molecular structure of both the SSIP and the CIP of any R2E=E′RM species (E=C, Si; E′=C, Si; M=metal).  相似文献   

20.
The complexes [Bu4N]2+[PtBr6]2− (I), [Ph4P]2+[PtBr6]2− (II), and [Ph3(n-Am)P]2+ (III) are synthesized by the reactions of tetrabutylammonium bromide, tetraphenylphosphonium bromide, and triphenyl(n-amyl)-tetraphenylphosphonium bromide, respectively, with potassium hexabromoplatinate (mole ratio 2: 1). After recrystallization from dimethyl sulfoxide, complexes I, II, and III transform into [Bu4N]+[PtBr5(DMSO)] (IV), [Ph4P]+[PtBr5(DMSO)] (V), and [Ph3(n-Am)P]+[PtBr5(DMSO)] (VI). According to the X-ray diffraction data, the cations of complexes IVVI have a slightly distorted tetrahedral structure. The N-C and P-C bond lengths are 1.492(7)–1.533(6) and 1.782(10)–1.805(10) ?, respectively. The platinum atoms in the mononuclear anions are hexacoordinated. The dimethyl sulfoxide ligands are coordinated with the Pt atom through the sulfur atom (Pt-S 2.3280(18)–2.3389(11) ?). The Pt-Br bond lengths are 2.4330(6)–2.4724(6) ?.  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