稀土4—甲基苯基化合物的合成

Hart等人利用苯基锂的乙醚溶液与无水稀土氯化物的四氢呋喃悬浮液反应,首次合成了稀土苯基化合物(C_6H_5)_3Ln(Ln=Sc,Y)。近年有人采用同法又合成了其它稀土苯基化合物(C_6H_5)_3Ln(Ln=Nd、Gd,Er,Yb),但均未得到满意的碳氢分析结果,碳的实测值约为计算值的2/3～3/4。Cotton等人报道了[Li(THF)_4][Lu{C_6H_3(CH_3)_2-2、6}4]的制备和晶体结构。为了进一步探索稀土芳基化合物的合成方法和成键可能性,我们选用苯     

稀土2-甲基苯基化合物的合成

Hart^[1][2]利用苯基锂的乙醚溶液与稀土氯化物的四氢呋喃悬浮液反应先后合成了稀土苯基化合物(C₆H₅)₃Ln(Ln=Sc,Y,Nd,Gd),但是没有得到满意的碳氢分析数据,碳的实测值仅为计算值的2/3左右,为了进一步探索稀土芳基化合物的合成方法以及稀土与芳基之间成键的可能性,我们使用2-甲基苯基锂与稀土氯化物进行反应,试图合成新的稀土芳基化合物。     

苯基稀土氯化物的合成及其表征

1970年,Hart等首先合成了Sc(C_6H_5)_3、Y(C_6H_5)_3、LiLa(C_6H_5)_4和LiPr(C_6H_5)_4。1972年,Cotton等测定了[Lu(2,6-(CH_3)_2C_6H_3)_4]·[Li·4THF]的晶体结构。1986年,陈文启等人合成了Nd(C_6H_5)_3,Gd(C_6H_5)_3和LiNd(C_6H_5)_4。本文首次合成了苯基稀土氯化物C_6H_5LnCl_2·nTHF(Ln=Pr,Sm,Gd,n=3,4);C_6H_5LnCl_2·LiCl·nTHF(Ln=Pr、Nd、Sm、Gd,n=2、3、5);(C_6H_5)_2GdCl·LiCl·2THF;[(C_6H_5)_2NdCl]_2·LiCl·4THF。测定了C_6H_5GdCl_2·4THF的晶体结构。     

稀土烯丙基化合物的研究 Ⅰ.镧、铈、镨、钕、钐和钇的烯丙基化合物的合成

Wilke等人报道了f-元素的烯丙基配合物Th(η~3-C_3H_5)_4的合成,之后Lug]i等人又制得U(η~3-C_3H_5)_4.Tsutsui和Ely首次合成了含有烯丙基的稀土金属配合物(η~5-C_5H_5)_2Ln(η~3-C_3H_5)(Ln=Sm、Er、Ho),并根据这些配合物的红外光谱在1533cm~(-1)出现共轭三碳的不对称伸缩振动吸收峰认为稀土离子是与烯丙基的非定域π-电子键合的.Mazzei介绍了二氧六环(C_4H_8O_2)的配合物,LiLn(C_3H_5)_4·C_4H_8O_2(Ln=Ce、Nd、Sm、Gd、Dy)的合成方法. 本文用无水稀土氯化物与烯丙基锂在四氢呋喃-乙醚中0℃反应,制得六个未见报道的稀土烯丙基化合物:     

配合物[Li(THF)_2]_2(μ—Cl)_4[(η~5—CH_3C_5H_4)Nd·THF]的合成及其晶体结构

环戊二烯基希土氯化物是一类合成希土有机配合物的重要前身。尽管在1980年前没能成功地合成含轻希土元素的这类配合物,但目前已发现,采用具有较大体积的取代环戊二烯做配体,如C_5Me_5H,C_5H_3〔Si(CH_3)_3〕_2H,C_5Me_4C_3H_7H和桥联的配体(C_5H_4)_2(CH_2)_3H_2都可得到相应的取代环戊二烯基轻希土氯化物。控制LnCl_3和CpNa的反应摩尔比也可以成功地得到这类轻希土的环戊二烯基氯化物。     

希土烯丙基化合物的研究——Ⅷ.镝、钬、铒、镱和镥的2-甲基烯丙基化合物的合成

用无水希土氯化物与2-甲基烯丙基氯化镁及四甲基乙二胺,0℃下,在四氢呋喃中反应,加乙醚后可得到五个含2-甲基烯丙基的重希土元素的化合物。经元素分析、红外光谱和质谱分析的鉴定,确定该化合物的组成为Ln(C_4H_7)_2Cl_5Mg_2(tmed)_2。     

希土硼氢化物的研究 Ⅹ.含[B_(10)H_9NH_2COCH=CH_2]~-的双苯甲酰丙酮缩1,3—丙二胺希土(Ⅲ)配合物的研究

将闭式+氢+硼酸阴离子酰胺衍生物[B_(10)H_9NH_2COCH=CH_2]~-、双苯甲酰丙酮缩1,3-丙二胺C_6H_5C(OH)=CHC(CH_3)=N(CH_3)CH=C(OH)C_6H_5(Bapn)及希土氯化物在丙酮-乙醇混合溶剂中进行反应,得到分子式为Ln(Bapn)_3[B_(10)H_9NH_2COCH=CH_2]_3(Ln=La,Nd,Sm,Eu,Gd,Dy)的混式配体希土配合物。通过元素分析、IR、~1H NMR及摩尔电导率的测定对配合物进行了表征,还通过DTA-TG方法研究了它们的热性质。     

二(环戊二烯基)氯化镨和二茚基稀土氯化物的合成

二(环戊二烯基)氯化镨的合成已知的二(环戊二烯基)稀土氯化物(C_5H_5)_2LnCl(Ln=Sm～Lu)均为重稀土化合物.曾有人试图合成二(环戊二烯基)轻稀土(Ln=La～Nd)氯化物但未获成功,认为是由于镧系收缩和轻稀土配位的不饱和性.然而,用取代环戊二烯基和茚基或含螯合物为配位体却可以合成轻稀土的化合物.我们采用 NdCl_3·2THF 和环戊二烯钠在 THF 溶液中室温下反应制得了(C_5H_5)_2NdCl·THF.它具有二聚体的结构,属单斜晶系,空间群为 P2_1/c,该化合物在抽空加热下脱 THF,得到组成符合(C_5H_5)_2NdCl 的残余物.     

含烯烃配体的过渡金属卡宾络合物的研究——Ⅺ.新型环己二烯(二羰基)[乙氧基(芳基)卡宾]铁络合物的异构化产物的合成、波谱和晶体结构

1,3-环己二烯(三羰基)铁(Ⅰ)与芳基锂,ArLi(Ar=C_6H_5,m-,p-CH_(?)C_6H_4,p-CH_3OC_6H_4,p-CF_3C_6H_4),在乙醚中低温下反应,所生成的酰羰基锂盐随后用Et_3OBF_4在水溶液中0℃烷基化,生成5个组成为C_6H_8(CO)_2Fec(OC_2H_5)Ar的橙红色结晶化合物(Ⅱ—Ⅵ)。根据元素分析,光谱研究和X射线品体结构测定,Ⅱ—Ⅵ为环己二烯(二羰基)[乙氧基(芳基)卡宾]铁络合物的异构化产物。本文报道和讨论了它们的合成、光谱和X射线衍射的研究结果,并探讨了可能的反应机制。#原图像不清楚     

2,4—二甲基戊二烯基稀土配合物的合成

通过元素分析、红外光谱、核磁共振谱、热重分析、晶体结构的测定以及对化合物水解产物的分析。确认合成了下列配合物: 〔η~5-2,4-(CH_3)_2C_5H_5〕LnCl_2·3THF(Ln=Nd,Sm,Gd), 〔η~5-2,4-(C_3H)_2C_5H_5〕_2LnCl·THF(Ln=Nd,Sm), 〔η~5-2,4-(CH_3)_2C_5H_5)_3Ln(Ln=La,Sm,Gd), (2,4-(CH_3)_2C_5H_5=2,4-二甲基戊二烯基。 THF=四氢呋喃     

Systematic investigation of lanthanide phosphonatoethanesulfonate framework structures by high-throughput methods, Ln(O3P-C2H4-SO3)(H2O) (Ln=La-Dy)

Following the strategy of using polyfunctional phosphonic acids for the synthesis of new metal phosphonates, the flexible organic linker molecule 2-phosphonoethanesulfonic acid, H2O3P-C2H4-SO3H (H3L), was used in a high-throughput (HT) investigation of lanthanide phosphonatoethanesulfonates. Two HT experiments comprising 96 individual hydrothermal reactions were performed to systematically investigate the influence of pH, rare earth ion, molar ratio of Ln3+:H3L, and the counterion in the system LnX3/H3L/NaOH/H2O with X=NO3-, Cl-, and CH3COO-. Whereas under basic conditions Ln(OH)3 is formed, acidic reaction conditions lead to nine isotypic compounds Ln(O3P-C2H4-SO3)(H2O) with Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), and Dy (9). The crystal size of the compounds is strongly dependent on the ionic radius of the lanthanides and the pH. No significant influence of the counterions of the rare earth salts is observed. For compounds 1, 2, 4, and 5 the crystal structures could be determined from single-crystal X-ray diffraction. The structures are built up from chains of edge-sharing LnO8 polyhedra that are connected by the phosphonate and sulfonate groups to layers. These layers are linked by the -CH2CH2- group to a three-dimensional framework. The compounds 6 and 8 display luminescence in the visible range (intensity maximum 612 and 544 nm, respectively). Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 270 degrees C. Furthermore IR, Raman, and solid-state MAS NMR spectra of 1 and magnetic property measurements of 7 are also presented.     

Bismuth coordination chemistry with allyl, alkoxide, aryloxide, and tetraphenylborate ligands and the {[2,6-(Me2NCH2)2C6H3]2Bi}+ cation

A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me(2)NCH(2))(2)C(6)H(3)](-) (Ar'), have been synthesized and structurally characterized to compare the coordination chemistry of Bi(3+) with similarly sized lanthanide ions, Ln(3+). Treatment of Ar'(2)BiCl, 1, with ClMg(CH(2)CH═CH(2)) affords the allyl complex Ar'(2)Bi(η(1)-CH(2)CH═CH(2)), 2, in which only one allyl carbon atom coordinates to bismuth. Complex 1 reacts with KO(t)Bu and KOC(6)H(3)Me(2)-2,6 to yield the alkoxide Ar'(2)Bi(O(t)Bu), 3, and aryloxide Ar'(2)Bi(OC(6)H(3)Me(2)-2,6), 4, respectively, but the analogous reaction with the larger KOC(6)H(3)(t)Bu(2)-2,6 forms [Ar'(2)Bi][OC(6)H(3)(t)Bu(2)-2,6], 6, in which the aryloxide ligand acts as an outer sphere anion. Chloride is removed from 1 by NaBPh(4) to form [Ar'(2)Bi][BPh(4)], 5, which crystallizes from THF in an unsolvated form with tetraphenylborate as an outer sphere counteranion.     

Syntheses, structures, and reactivities of homometallic rare-earth-metal multimethyl methylidene and oxo complexes

Unsolvated, trinuclear, homometallic, rare-earth-metal multimethyl methylidene complexes [{(NCN)Ln(μ(2)-CH(3))}(3)(μ(3)-CH(3))(μ(3)-CH(2))] (NCN = L = [PhC{NC(6)H(4)(iPr-2,6)(2)}(2)](-); Ln = Sc (2a), Lu (2b)) have been synthesized by treatment of [(L)Ln{CH(2)C(6)H(4)N(CH(3))(2)-o}(2)] (Ln = Sc (1a), Lu (1b)) with two equivalents of AlMe(3) in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe(3) gives the heterometallic trinuclear complexes [(L)Ln(AlMe(4))(2)] (Ln = Sc (3a), Lu (3b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce C-H bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo-trimethyl complexes [{(L)Ln(μ(2) -CH(3))}(3) (μ(3)-CH(3))(μ(3)-O)] (Ln = Sc(4a), Lu(4b)) in high yields. Complex 4b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ(2) -CH(3) )}(3) (μ(3) -OC(6)H(9))(μ(3)-O)] (5b), whereas reaction of 4b with acetophenone forms the insertion product [{(L)Lu(μ(2)-CH(3))}(3){μ(3)-OCPh(CH(3))(2)}(μ(3)-O)] (6b). Complex 4a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X-ray diffraction determination.     

Fine-tuning of lanthanide-monocarboxylate coordination networks through ligand decoration

We report herein five new coordination polymers of general formula [LnNa(C(6)H(5)CO(2))(4)] where Ln = Y (6), Tb (7), Er (8), [DyNa(CH(3)CO(2))(4)(MeOH)] (9) and [DyNa(C(3)H(7)CO(2))(4)] (10). Single crystal structure analyses revealed that all compounds have a repeating unit containing one Ln(3+), one Na(+) and four monocarboxylate ligands (RCO(2)(-)) (R = -CH(3), -C(3)H(7), -C(6)H(5)). Compounds 6-8 and 10 possess helical polymeric structures which are extended in three dimensions forming chiral srs networks whilst compound 9 constitutes a two dimensional honeycomb network, illustrating that variation in the alkyl group of the monocarboxylate can result in versatile and variable polymeric networks. The magnetic properties of the reported compounds have also been studied.     

Lower homologues (methyl, ethyl) of diorganotin derivatives of germyl (substituted) propanoic acids: spectroscopic elucidations and biological studies

Some novel lower homologues of diorganotin derivatives of germyl substituted propanoic acids with general formula [Ar(3)GeCH(R(1))CH(R(2))COO](2)SnR(2)(3), where Ar = p-CH(3)C(6)H(4), C(6)H(5), R(1) = p-CH(3)C(6)H(4), p-CH(3)OC(6)H(4), o-CH(3)OC(6)H(4), C(6)H(5), R(2) = H, CH(3), R(3) = CH(3), C(2)H(5) have been prepared by the condensation reaction of dialkyltin oxide and triarylgermyl(substituted) propanoic acid in 1 : 2 M ratio, respectively, and were characterized by IR, multinuclear ((1)H, (13)C, (119)Sn) NMR, (119 m)Sn M?ssbauer spectroscopy. The synthesized compounds were also screened for their toxicity and possible antibacterial, antifungal activities and found some encouraging results.     

含茂基、烷氧基及氯离子混合配镧系金属有机化合物的合成及表征

本文通过二茂基镧不金属氯化物Ｃｐ２ＬｎＣｌ（Ｃｐ＝Ｃ５Ｈ５；Ｌｎ＝Ｄｙ，Ｙｂ）与烷基醇ＲＯＨ（Ｒ＝－ＣＨ２ＣＨ２ＣＨ３，－ＣＨ２ＣＨ＝ＣＨ２）在四氢呋喃中反应，合成了四个新的含三种不同配位基的镧系金属有机化合物；元素分析，红外光谱及质谱分析表明这些化合物可能具有三聚体结构，即：［ＣｐＬｎ（ＯＲ）Ｃｌ］３。     

Attempted syntheses of lanthanide(III) complexes of the anisole- and anilinosquarate ligands

The polymeric lanthanide complexes (Ln(mu-CH3OC6H5C4O3)(CH3OC6H5C4O3)2 (H2O)4.xH2O)n [Ln=La (1), Eu (2), Gd (3)], formed from the reaction of aqueous solutions of anisolesquarate and Ln(NO3)3.xH2O, are all structurally similar with only subtle differences between the lanthanum complex and the isomorphous pair of europium and gadolinium analogues. The lanthanum atom in 1 has a square antiprismatic coordination geometry comprising two pendant and two mu-1,3-bridging anisolesquarate groups and four aqua ligands. Complexes 2 and 3 have two independent metal atoms in their asymmetric units compared to one for the lanthanum complex. However, the gross structures of 1-3 are essentially the same. The asymmetric unit of the terbium complex ((CH3OC6H5C4O3)3Tb(H2O)4(mu-CH3OC6H5C4O3)(CH3OC6H5C4O3)2Tb(H2O)5).H2O (4) contains two independent binuclear units which hydrogen bond to form an extended structure very similar to those of 1-3. The ionic polymers ([Ln(mu2-C4O4)(H2O)6][C6H5NHC4O3].4H2O)n [Ln=Eu (5), Gd (6), Tb (7)] result from the incomplete hydrolysis of the anilinosquarate ion during the attempted synthesis of Eu(III), Gd(III), and Tb(III) anilinosquarate complexes. However, complete hydrolysis of the substituent is accomplished by La(III) ions, and the neutral polymer (La2(mu2-C4O4)2(mu3-C4O4)(H2O)11.2H2O)n (8) is formed. In complexes 5-7, the central lanthanide atom has a square antiprismatic geometry, being bonded to two mu-1,2-bridging squarate and six aqua ligands. Two anilinosquarate counteranions participate in second-sphere coordination via direct hydrogen bonding to aqua ligands on each metal center. These counteranions, and the included waters of crystallization, serve to link neighboring cationic polymer chains via an extensive array of O-H...O hydrogen bonds to form a 3-dimensional network. The polymeric lanthanum complex 8 contains two different metal environments, each having distorted monocapped square antiprismatic geometry. For one lanthanum atom the coordination polyhedron comprises five aqua and four squarate ligands, while for the other the polyhedron consists of six aqua and three squarate ligands; in each case one of the aqua ligands occupies the capping position. The squarate ligand exhibits two coordination modes in 8 (mu-1,2- and mu-1,3-bridging), and neighboring polymer chains are cross-linked by hydrogen bonds to form a 3-dimensional network.     

Aluminium complexes containing bidentate and symmetrical tridentate pincer type pyrrolyl ligands: synthesis, reactions and ring opening polymerization

A series of aluminium derivatives containing substituted bidentate and symmetrical tridentate pyrrolyl ligands, [C(4)H(3)NH(2-CH(2)NH(t)Bu)] and [C(4)H(2)NH(2,5-CH(2)NH(t)Bu)(2)], in toluene or diethyl ether were synthesized. Their reactivity and application for the ring opening polymerization of ε-caprolactone have been investigated. The reaction of AlMe(3) with one equiv. of [C(4)H(3)NH(2-CH(2)NH(t)Bu)] in toluene at room temperature affords [C(4)H(3)N(2-CH(2)NH(t)Bu)]AlMe(2) (1) in 70% yield by elimination of one equiv. of methane. Interestingly, while reacting AlMe(3) with one equiv. of [C(4)H(3)NH(2-CH(2)NH(t)Bu)] in toluene at 0 °C followed by refluxing at 100 °C, [{C(4)H(3)N(2-CH(2)N(t)Bu)}AlMe](2) (2) has been isolated via fractional recrystalliztion in 30% yield. Similarly, reacting AlMe(3) with two equiv. of C(4)H(3)NH(2-CH(2)NH(t)Bu) generates [C(4)H(3)N(2-CH(2)NH(t)Bu)](2)AlMe (3) in a moderate yield. Furthermore, complex 1 can be transformed to an aluminium alkoxide derivative, [C(4)H(3)N(2-CH(2)NH(t)Bu)][OC(6)H(2)(-2,6-(t)Bu(2)-4-Me)]AlMe (4) by reacting 1 with one equiv. of HOC(6)H(2)(-2,6-(t)Bu(2)-4-Me) in toluene via the elimination of one equiv. of methane. The reaction of AlR(3) with one equiv. of [C(4)H(2)NH(2,5-CH(2)NH(t)Bu)(2)] in toluene at room temperature affords [C(4)H(2)N(2,5-CH(2)NH(t)Bu)(2)]AlR(2) (5, R = Me; 6, R = Et) in moderate yield. Surprisingly, from the reaction of two equiv. of [C(4)H(2)NH(2,5-CH(2)NH(t)Bu)(2)] with LiAlH(4) in diethyl ether at 0 °C, a novel complex, [C(4)H(2)N(2-CH(2)N(t)Bu)(5-CH(2)NH(t)Bu)](2)AlLi (7) has been isolated after repeating re-crystallization. Furthermore, reacting one equiv. of C(4)H(2)NH(2,5-CH(2)NH(t)Bu)(2) with AlH(3)·NMe(3) in diethyl ether generates an aluminium dihydride complex, [C(4)H(2)N(2,5-CH(2)NH(t)Bu)(2)]AlH(2) (8), in high yield. Additionally, treating 8 with one equiv. of HOC(6)H(2)(-2,6-(t)Bu(2)-4-Me) in methylene chloride produces [C(4)H(2)N(2,5-CH(2)NH(t)Bu)(2)][OC(6)H(2)(-2,6-(t)Bu(2)-4-Me)]AlH (9) with the elimination of one equiv. of H(2). The aluminium alkoxide complex 4 shows moderate reactivity toward the ring opening polymerization of ε-caprolatone in toluene.     

Syntheses and reactions of hexavalent organotellurium compounds bearing five or six tellurium-carbon bonds

A variety of hexaorganotellurium compounds, Ar(6-n)(CH3)nTe [Ar=4-CF3C6H4, n=0 (1a), n=1 (3a), n=2 (trans-4a and cis-4a), n=3 (mer-5a), n=4 (trans-6a); Ph, n=0 (1b), n=1 (3b), n=2 (trans-4b); 4-CH3C6H4, n=0 (1c), n=1 (3c), n=2 (trans-4c), n=4 (trans-6c); 4-BrC6H4, n=0 (1d)] and Ar5(R)Te [Ar=4-CF3C6H4, R=4-CH3OC6H4 (8); Ar=4-CF3C6H4, R=vinyl (9), Ar=Ph, R=vinyl (10), Ar=4-CF3C6H4, R=PhSCH2 (11), Ar=Ph, R=PhSCH2 (12), Ar=4-CF3C6H4, R=nBu (13)] and pentaorganotellurium halides, Ar5TeX [Ar=4-CF3C6H4, X=Cl (2a-Cl), X=Br (2a-Br); Ar=Ph, X=Cl (2b-Cl), X=Br (2b-Br); Ar=4-CH3C6H4, X=Cl (2c-Cl), X=Br (2c-Br); Ar=4-BrC6H4, X=Br (2d-Br)] and (4-CF3C6H4)4(CH3)TeX [X=Cl (trans-7a-Cl) and X=Br (trans-7a-Br)] were synthesized by the following methods: 1) one-pot synthesis of 1 a, 2) the reaction of SO2Cl2 or Br2 with Ar5Te(-)Li+ generated from TeCl4 or TeBr4 with five equivalents of ArLi, 3) reductive cleavage of Ar(6-m)(CH3)(m)Te (m=0 or 2) with KC8 followed by treatment with CH3I, 4) valence expansion reaction from low-valent tellurium compounds by treatment with KC8 followed by reaction with CH3I, 5) nucleophilic substitution of Ar(6-y-z)(CH3)zTeX(y-z) (X=Cl, Br, OTf; z=0, 1; y=1, 2) with organolithium reagents. The scope and limitations and some details for each method are discussed and electrophilic halogenation of the hexaorganotellurium compounds is also described.     

Asymmetric allylic amination in water catalyzed by an amphiphilic resin-supported chiral palladium complex

[reaction: see text] Catalytic asymmetric allylic amination of cycloalkenyl carbonates (methyl cyclohexen-2-yl carbonate, methyl cyclohepten-2-yl carbonate, methyl 5-methoxycarbonylcyclohexen-2-yl carbonate, methyl cyclohexenyl carbonate, tert-butyl 5-methoxycarbonyloxy-1,2,5,6-tetrahydropyridinedicarboxylate) with dibenzylamines ((C6H5CH2)2NH, (C6H5CH2)(4-CH3OC6H4CH2)NH, (4-CH3OC6H4CH2)2NH) was achieved in water under heterogeneous conditions by use of a palladium complex of (3R,9aS)-3-[2-(diphenylphosphino)phenyl]-2-phenyltetrahydro-1H-imidazo[1,5-a]indole-1-one anchored on polystyrene-poly(ethylene glycol) copolymer resin to give the corresponding cycloalkenylamines with high enantiomeric selectivity (90-98% ee).