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.
Mononuclear copper(II) complexes of a family of pyridylmethylamide ligands HL, HLMe, HLPh, HLMe3 and HLPh3, [HL = N-(2-pyridylmethyl)acetamide; HLMe = N-(2-pyridylmethyl)propionamide; HLPh = 2-phenyl-N-(2-pyridylmethyl)acetamide; HLMe3 = 2,2-dimethyl-N-(2-pyridylmethyl)propionamide; HLPh3 = 2,2,2-triphenyl-N-(2-pyridylmethyl)acetamide], were synthesized and characterized. The reaction of copper(II) salts with the pyridylmethylamide ligands yields complexes [Cu(HL)2(OTf)2] (1), [Cu(HLMe)2](ClO4)2 (2), [Cu(HL)2Cl]2[CuCl4] (3), [Cu(HLMe3)2(THF)](OTf)2 (4), [Cu(HLMe3)2(H2O)](ClO4)2 (5a and 5b), [Cu(HLPh3)2(H2O)](ClO4)2 (6), [Cu(HL)(2,2′-bipy)(H2O)](ClO4)2 (7), and [Cu(HLPh)(2,2′-bipy)(H2O)](ClO4)2 (8). All complexes were fully characterized, and the X-ray structures vary from four-coordinate square-planar, to five-coordinate square-pyramidal or trigonal-bipyramidal. The neutral ligands coordinate via the pyridyl N atom and carbonyl O atom in a bidentate fashion. The spectroscopic properties are typical of mononuclear copper(II) species with similar ligand sets, and are consistent their X-ray structures.  相似文献   

2.
Yang D  Gao Q  Lee OY 《Organic letters》2002,4(7):1239-1241
[reaction: see text] A new Lewis acid promoted phenylseleno group transfer tandem radical cyclization method was developed. In the presence of Lewis acids such as Yb(OTf)3 or Mg(ClO4)2, under photolysis condition at low temperature (-45 degrees C), various unsaturated alpha-phenylseleno beta-keto amides underwent radical cyclization reactions to give monocyclic or bicyclic products in a highly efficient, regioselective, and stereoselective manner.  相似文献   

3.
The reaction of Sb(NMe2)3 with aldehydes and ketones leads to enamines or diamines according to the degree of substitution of the carbonyl compound. With acids Sb(NMe2)3 gives amides, and with β-diketones and β-keto esters it gives enamines. With bifunctional compounds such as diols, secondary diamines or aminoalcohols, different heterocyclic compounds are formed according to the ratio of bifunctional compound to antimony.  相似文献   

4.
(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)3 yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.  相似文献   

5.
The catalytic activity of two manganese(III)-oxazoline complexes [Mn(phox)2(CH3OH)2]ClO4 and Mn(phox)3 (Hphox = 2-(2′-hydroxylphenyl)oxazoline), was studied in the epoxidation of various olefins. All of epoxidation reactions were carried out in (1:1) mixture of methanol:dichloromethane at room temperature using urea hydrogen peroxide (UHP) as oxidant and imidazole as co-catalyst. The epoxide yields clearly demonstrate the influence of steric and electronic properties of olefins, the catalysts and nitrogenous bases as axial ligand. [Mn(phox)2(CH3OH)2]ClO4 catalyst with low steric properties has higher catalytic activity than Mn(phox)3. The highest epoxide yield (95%) was achieved for indene at the presence of [Mn(phox)2(CH3OH)2]ClO4 within 5 min. The proximal and distal interactions of strong π-donor axial ligands such as imidazole with the active intermediate are efficiently increased activity of the catalytic system.  相似文献   

6.
Four dinuclear amino acid cadmium(Ⅱ) complexes [Cd2(tren)2(dl-alaninato)](ClO4)3·H2O(Ⅰ), [Cd2(tren)2·(l-alaninato)](ClO4)3·H2O(Ⅱ), [Cd2(tren)2(dl-phenylalaninato)](ClO4)3(Ⅲ) and [Cd2(tren)2(l-phenylalaninato)]· (ClO4)3(Ⅳ), constructed from mixed ligands of tris(2-aminoethyl)amine(tren) and racemic or natural amino acids( amino acids=dl- or l-alanine, and dl- or l-phenylalanine), have been synthesized and characterized by X-ray crystallography. The structural analysis of complexes Ⅰ and Ⅲ reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual (N,O,O′)-bridged mode, resulting in asymmetric chromophores of CdN4O and CdN5O in complex Ⅰ, CdN4O2 and CdN5O in complex Ⅲ, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the diastereoselectivity of the reaction favors the formation of the syn-isomers.  相似文献   

7.
Dan Wang  Shi-Xiong Liu   《Polyhedron》2007,26(18):5469-5476
Reactions among Cu(ClO4)2 · 6H2O, Cu(acac)2/VO(acac)2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu2L(acac)(H2O)2]ClO4 (1), [Cu4L2(acac)2(py)2](ClO4)2 (2) and (VO2)2L2Cu2(acac)2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO4 anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1.  相似文献   

8.
Enantioselective chlorination of b-keto esters and amides catalyzed by squaramide-linked bisoxazoline ligand–Cu(OAc)2complexes was investigated. The corresponding chlorinated products were obtained in excellent yields with moderate enantioselectivities. The effect of solvent, temperature, Lewis acid, and ligand structure on the reaction is discussed. This was the first investigation of catalytic asymmetric achlorination of b-keto amides. This study has highlighted that a simple chiral squaramide–oxazoline with cheap Cu(OAc)2 H2 O complexes can catalyze this chlorination.  相似文献   

9.
A potentially decadentate ligand, 1,1,4,7,10,10-hexakis(3,5-dimethyl-1-pyrazolylmethyl)-1,4,7,10-tetraazadecane (tthd), has been synthesized from the reaction of tri-ethylenetetramine with six equivalents of N-hydroxymethyl-3,5-dimethylpyrazole. The tthd ligand forms coordination compounds, M2(tthd)(ClO4)4(H2O)x, when M is Co, Ni, Cu, Zn and Cd and x = 4–8; and M2(tthd)(A)2(ClO4)2(H2O)x when M is Co and Ni, A is NCS or Cl, and x = 4–8. The cobalt compound, Co2(tthd)(ClO4)2(H2O)2(MeOH)1.75, crystallizes in the triclinic space group P1, a = 1.959(2), b = 1.5657(3), c = 2.1244(3) nm, = 105.5(1), β = 96.9(1), γ = 112.1(1). Due to severe disorder of the anions the structure could only be refined to an Rw, value of 0.099. The ligand acts as a decadentate, dinucleating ligand. The cobalt ions are distorted octahedrally surrounded by five N-atoms of the tthd ligand and an O-atom of water occupying the sixth coordination place. The other perchlorate compounds have very similar structures, as can be concluded from spectroscopic data.

In the thiocyanate and chloride compounds the anions have replaced the coordinated water molecules, resulting in octahedral Ni compounds. With Co thiocyanate, however, tthd acts as an octadentate ligand, resulting only in five-coordinated compounds.  相似文献   


10.
To examine the steric effects on the stability of Ln(0) π-arene compounds, molecular mechanics (MMP2) calculations are performed on Gd(η-C6H6)2 and Ln(η-But3C6H3)2 (where Ln is Gd, Yb and Y ). The small potential-well depth ( ≈ 2 kcal mol−1) and the large Gd-C equilibrium distance ( > 3.3 Å) explains the instability of Gd(η-C6H6)2, while the difference in the stability between Gd(η-But3C6H3)2 and Yb(η-But3C6H3)2 can be attributed to the difference in the van der Waalsradii of the two metals and the more contracted 5d orbitals on the Yb atom.  相似文献   

11.
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η4-C4H4R2)(CH3)2, where Cp=η5-C5H5 and R=H or CH3, with equimolar amounts of B(C6F5)3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3], indicate that the borane attack has occurred at the methyl position.  相似文献   

12.
Samarium complexes with glutamic acid containing cationic [Sm2(Glu)2(H2O)8]4+ units have been prepared and characterized by using elemental analysis, infrared absorption spectra and thermal analysis. In addition, the crystal and molecular structure of [Sm2(Glu)2(H2O)8](ClO4)4·3H2O was determined by X-ray diffraction. The presence of glutamic acid in the Sm coordination sphere allows the formation of a singular extended 2D arrangement. Sm atoms are nine coordinated, in a monocapped square antiprism geometry. They are connected by means of different μ-COO bridges, involving - and γ-carboxylate groups of the amino acid.  相似文献   

13.
Recent results (post-1990) on the synthesis and structures of bis(trimethylsilyl)methyls M(CHR2)m (R = SiMe3) of metals and metalloids M are described, including those of the crystalline lipophilic [Na(μ-CHR2)], [Rb(μ-CHR2)(PMDETA)]2, K4(CHR2)4(PMDETA)2, [Mg(CHR2)(μ-CHR2)], P(CHR2)2 (gaseous) and P2(CHR2)4, [Yb(CHR2)2(OEt2)2] and [{Yb(CR3)(μ-OEt)(OEt2)}2]; earlier information on other M(CHR2)m complexes and some of their adducts is tabulated. Treatment of M(CHR2) (M = Li or K) with four different nitriles gave the X-ray-characterized azaallyls or β-diketinimates , and (LL′ = N(R)C(tBu)CHR, L′L′ = N(R)C(Ph)C(H)C(Ph)NR, LL″ = N(R)C(Ph)NC(H)C(Ph)CHR, R = SiMe3 and Ar = C6H3Me2-2,5). The two lithium reagents were convenient sources of other metal azaallyls or β-diketinimates, including those of K, Co(II), Zr(IV), Sn(IV), Yb(II), Hf(IV) and U(VI)/U(III). Complexes having one or more of the bulky ligands [LL′], [L′L′], [LL], [LL″], [L″L], [LL] and [{N(R)C(tBu)CH}2C6H4-2]2− are described and characterized (LL = N(H)C(Ph)C(H)C(Ph)NH, L″L = N(R)C(tBu)C(H)C(Ph)NR, LL = N(R)C(tBu)CHPh). Among the features of interest are (i) the contrasting tetrahedral or square-planar geometry for and , respectively, and (ii) olefin-polymerization catalytic activity of some of the zirconium(IV) chlorides.  相似文献   

14.
Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe3)2}2, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe3)2]·THF and M[N(SiMe3)2]2·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe3)2]2·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me3Si)2NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH2CH2O)nCH=CH2 (n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from 1H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol.  相似文献   

15.
Dennis P. Arnold 《Polyhedron》1986,5(12):1957-1963
Visible absorption and 1H NMR spectra have been measured for a series of octahedral tin(IV) porphyrin complexes Sn(TPP)X2, where TPP is mes-tetraphenylporphyrin and X is Cl, OH, OMe, OAc, NO3, ClO4, Br, I, NCS and OC6H4-p-Me. The tin-proton coupling constants to the β-pyrrole protons decrease from 19.2 Hz (X = ClO4) to 9.9 Hz (X = OME), and for the oxygen-bound ligands, correlate well with the basicity of the ligands. The halides do not fit this relationship, perhaps because of π-bonding effects. The chemical shifts of the β-protons also depend on the nature of X, and vary from 9.35 (X = ClO4) to 9.04 (X = OC6H4-p-Me) ppm. Increasing basicity of X causes red shifts in the visible spectra, as well as a decrease in the molar absorption coefficient ratio (β/) for the visible absorption bands. Tin-proton coupling constants for the axial ligands OH, OMe and OAc are reported. The complex Sn(TPP)(ClO4)2 exhibits unusual NMR behaviour in CDCl3 solutions, possibly due to self-aggregation.  相似文献   

16.
A series of luminescent rhenium(I) monoynyl complexes, [Re(N---N)(CO)3(CC---R)] (N---N=bpy, tBu2bpy; R=C6H5, C6H4---Cl-4, C6H4---OCH3-4, C6H4---C8H17-4, C6H4---C6H5, C8H17, C4H3S, C4H2S---C4H3S, C5H4N), together with their homo- and hetero-metallic binuclear complexes, {Re(N---N)(CO)3(CC---C5H4N)[M]} (N---N=bpy, tBu2bpy; [M]=[Re{(CF3)2-bpy}(CO)3]ClO4, [Re(NO2-phen)(CO)3]ClO4, W(CO)5) have been synthesized and their electrochemical and photoluminescence behaviors determined. The structural characterization and electronic structures of selected complexes have also been studied. The luminescence origin of the rhenium(I) alkynyl complexes has been assigned as derived states of a [dπ(Re)→π*(N---N)] metal-to-ligand charge transfer (MLCT) origin mixed with a [π(CCR)→π*(N---N)] ligand-to-ligand charge transfer (LLCT) character. The assignments are further supported by extended Hückel molecular orbital (EHMO) calculations, which show that the LUMO mainly consists of π*(N---N) character while the HOMO is dominated by the antibonding character of the Re---CCR moiety resulted from the overlap of the dπ(Re) and π(CCR) orbitals.  相似文献   

17.
The dialkynyl complexes cis-[Pt(C CR)2L2] [R = Ph, L2 = 2PPh3, 2PEt3, dppe (dppe = 1,2-bis(diphenylphosphino)ethane]; R ---tBu, L2 = 2PPh3, dppe) react with silver perchlorate in a molar ratio 1:0.5 to give platinum-silver perchlorate salts of the type [Pt2 Ag(C CR)4L4](ClO4) in excellent yield. The X-ray crystal structure of [Pt2Ag(C = CPh)4(PPh3)4](ClO4) 1 shows that the cation is formed by two nearly orthogonal cis-[Pt(C CPh)2(PPh3)2] units connected through a silver cation which is unsymmetrically π-bonded to all four acetylene fragments. Similar reactions of cis-[Pt(C CR)2L2] with one equivalent of AgClO4 afford cationic complexes of general formula [PtAg(C CR)2L2](ClO4), which are believed to be salts, [Pt2Ag2(C CR)4L4](ClO4)2.  相似文献   

18.
Four novel tetranuclear macrocyclic complexes of the formula [(CuLi)3Fe](ClO4)3·3H2O (i=1–4, Li are the dianions of the [14]N4 and [15]N4 macrocyclic oxamides, namely 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene, 2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene and 2,3-dioxo-5,6:14,15-dibenzo-7,13-bis(ethoxycarbonyl)-1,4,8,12-tetraazacyclotetradeca-7,12-diene] have been prepared and characterized. These complexes are the first examples of oxamido-bridged Cu(II)–Fe(III) heterometallic species. Cryomagnetic studies on [(CuL1)3Fe](ClO4)3·3H2O (1) and [(CuL3)3Fe](ClO4)3·3H2O (3) (77–300 K) revealed that the Cu(II) and Fe(III) ions interact antiferromagnetically through the oxamido bridge, with the exchange integral J=−30.8 cm−1 for 1 and J=−28.7 cm−1 for 3 based on . The interaction parameters have been compared with that of the related [Cu3Mn] compound.  相似文献   

19.
The chiral bis-imine (1R,2R)-C6H10-[E---N=CH---C6H3---3,4-(OMe)2]2 1 (LH) reacts with [Pd(OAc)2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)-C6H10---N=CH---C6H3-3′,4′-(OMe)2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N,N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO4) (L′=PPh3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl3 giving [Pd(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)(PPh3)](ClO4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH2Cl2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the Caryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac-O,O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO4) 12, while classical N,N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ1-N-phen)](ClO4) 10 and [Pd(L-κ-C,N,N)(κ1-N-bipy)](ClO4) 11. Treatment of 1 with PtCl2(DMSO)2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl2Pt[(NH2)2C6H10---N,N′] 13a and [Pt(Cl)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η3-2-Me---C3H4)]2 with 1 in refluxing CHCl3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity.  相似文献   

20.
通过熔融共混将三氟甲烷磺酸镱[Yb(OTf)3]和三氟甲烷磺酸镧[La(OTf)3]添加至聚丙烯(PP)中, 制得PP/Yb和PP/La材料, 并对其热稳定性进行表征. 热失重分析(TGA)和差示扫描量热分析(DSC)结果显示, Yb(OTf)3和La(OTf)3均可以显著提高聚丙烯的热稳定性. 当Yb(OTf)3添加量仅为1%(质量分数)时, PP的起始分解温度从275 ℃提高至305 ℃, 最大分解温度从384 ℃提高至405 ℃, 160 ℃下的氧化诱导时间从12.1 min延长至43.0 min, 热焓从1907 J/g降低至483 J/g; 而PP/La1的起始分解温度、 最大分解温度、 160 ℃下的氧化诱导时间和热焓分别为300 ℃, 409 ℃, 18.6 min和633 J/g. 结果表明, La(OTf)3对聚丙烯热稳定性的改善作用弱于Yb(OTf)3, 对2种稀土盐产生不同实验结果的原因进行分析并提出机制. 由于阴离子和阳离子的共同作用, Yb(OTf)3和La(OTf)3均可提高PP的热氧稳定性. La(OTf)3中三氟甲烷磺酸根的自由基捕捉能力和稀土离子的配位能力发挥主要作用, 而Yb(OTf)3中的稀土离子的高反应活性也起到关键作用.  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