Synthesis and reactivity of rare earth metal alkyl complexes stabilized by anilido phosphinimine and amino phosphine ligands

Anilido phosphinimino ancillary ligand H2L1 reacted with one equivalent of rare earth metal trialkyl [Ln{CH2Si(CH3)(3)}(3)(thf)(2)] (Ln = Y, Lu) to afford rare earth metal monoalkyl complexes [L(1)LnCH(2)Si(CH3)(3)(THF)] (1a: Ln = Y; 1b: Ln = Lu). In this process, deprotonation of H2L1 by one metal alkyl species was followed by intramolecular C-H activation of the phenyl group of the phosphine moiety to generate dianionic species L-1 with release of two equivalnts of tetramethylsilane. Ligand L-1 coordinates to Ln(3+) ions in a rare C,N,N tridentate mode. Complex 1a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL1)LnY(NHC(6)H(3)iPr(2)-2,6)(2)] (2) selectively, that is, the C-H activation of the phenyl group is reversible. When 1a was exposed to moisture, the hydrolyzed dimeric complex [{(HL1)Y(OH)}(2)](OH)(2) (3) was isolated. Treatment of [Ln{CH2Si(CH3)(3)}(3)-(thf)(2)] with amino phosphine ligands HL2-R gave stable rare earth metal bisalkyl complexes [(L2-R)Ln{CH2Si(CH3)(3)}(2)(thf)] (4a: Ln=Y, R=Me; 4b: Ln=Lu, R=Me; 4c: Ln=Y, R=iPr; 4d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4a and 4c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L2-R)Y(NHC(6)H(3)iPr(2)-2,6)(2)(thf)] (5a: R=Me; 5b: R=iPr).

Rare earth metal bis(alkyl) complexes bearing amino phosphine ligands: Synthesis and catalytic activity toward ethylene polymerization

Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)(2) (HL1) and Lu(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h generated mono(alkyl) complex (L-1)(2)Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)(2) (HL2) with Lu(CH2SiMe3)(3)(THF)(2) afforded (L-2)(2)Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L-2)(3)Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)(2) (HL3) swiftly reacted with Ln(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L(3)Ln(CH2SiMC3)(2)(THF)(n) (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and [Ph3C][B(C6F5)(4)], was able to catalyze the polymerization of ethylene to afford linear polyethylene.

Synthesis, structure and norbornene polymerization behavior of nickel complexes bearing two beta-ketoiminato chelate ligands

A series of nickel(II) complexes bearing two nonsymmetric bidentate beta-ketoiminato chelate ligands have been prepared, and the structures of complexes [(2,6-Me2C6H3)NC(CH3)C(H)C(Ph)O](2)Ni (4a) and [(2,6-Me2C6H3)NC(CH3)C(H)C(CF3)O](2)Ni (4c) have been confirmed by X-ray crystallographic analysis. These nickel(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce high molecular weight polymers. Catalytic activity of up to 1.16 x 10(4) kg/mol(Ni) .h and the viscosity-average molecular 9 weight of polymer of up to 870 kg/mol were observed. Catalyst activity, polymer yield, and polymer molecular weight could be controlled over a wide range by the variation of the reaction parameters such as Al/Ni molar ratio, norbornene/catalyst molar ratio, monomer concentration, polymerization reaction temperature and time.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization

A series of binuclear neutral nickel and palladium complexes [(XC6H2CH=NC6H3-iPr(2))MRL](2) 4b-f (X=NO2, M=Ni, R=Ph, L=PPh3, 4b; X=H, M=Pd, R=Me, L=PPh3,4c; X=H,M=Pd, R=Me, L=Py, 4d; X=NO2,M=Pd, R=Me, L=PPh3, 4e; X=NO2, M=Pd, R=Me, L=Py, 4f) and [(C10H7CH=NC6H3-iPr(2))MRL](2) 8a-c (M=Ni, R=Ph, L=PPh3, 8a; M=Pd, R=Me, L=PPh3, 8b; M=Pd, R=Me, L=Py, 8c) have been synthesized and characterized. The structures of complexes 4e and 8b have also been confirmed by X-ray crystallographic analysis. With modified methylalummoxane (MMAO) as cocatalysts, these complexes and complex [(C6H3CH=NC6H3-iPr(2))NiPh(PPh3)](2) 4a are capable of catalyzing the addition polymerization of norbomene (NBE) with the high activity up to 2.3 x 10(8) g PNBE/(mol(M) h). The structure of complexes affects considerably catalytic activity towards norbomene polymerization. The polymers obtained with nickel complexes are soluble, while those obtained with palladium complexes are insoluble. Palladium complexes 4c, 4e and 8b bearing PPh3 ligands exhibit much higher activities than the corresponding complexes 4d, M and 8c bearing pyridine ligands under the same conditions.

Syntheses, structure and ethylene polymerization behavior of beta-diiminato titanium complexes

A series of new titanium complexes bearing beta-diiminato ligands [(Ph)NC(R-1)CHC(R-2)N(Ph)](2)TiCl2 (4a: R-1 = R-2 = CH3; 4b: R-1 = R-2 = CF3; 4c: R-1 = Ph, R-2 = CH3; 4d: R-1 = Ph, R-2 = CF3) has been synthesized and characterized. X-ray crystal structures reveal that complexes 4a and 4c adopt distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-d are active catalysts for ethylene polymerization, and produce high molecular weight polyethylenes. Catalyst activities and the molecular weights of polymers are considerably influenced by the steric and electronic effects of substituents on the catalyst backbone under the same polymerization condition. With the strong electron-withdrawing groups (CF3) at R-1 or/and R-2 position, complexes 4b and 4d show higher activities than complexes 4a and 4c, respectively.

Synthesis and structural characterization of a new molecule-based complex constructed from dodecamolybdophosphoric acid and imidazole

A new compound, (CH5N2)(3)(PMo12O40CH4N23H2O)-C-.-H-. (1), was synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra, NMR spectra and ESR spectra. This is, to our knowledge, the first example of an imidazole-polyoxometalate species. The compound was recrystallized from N,N-dimethylformamide (DMF), and then black block-like crystals of (C3H5N2)(4)((PMoMo11O40)-Mo-V-O-VI)(.)4C(3)H(7)NO(.) 2H(2)O (2), were obtained. It crystallizes in a triclinic space group P (1) over bar with n=12.423(3) Angstrom, b=12.666(3) Angstrom, c=13.341(3) Angstrom, alpha=70.56(3)degrees, beta=71.16(3)degrees, gamma=64.18(3)degrees, V= 1742.3(6) Angstrom(3), Z=1, R1 = 0.0585, wR2 = 0.1885. An X-ray crystallographic study showed that the crystal structure is constructed by electrostatic attractions and hydrogen bonds between a dodecamolybdophosphoric anion and an imidazole. The imidazole and DMF molecules occupy cavities in a polyoxometalate lattice ordered along a c-axis. The structure of (2) is similar to that of (1) from a comparison of both IR spectra and TGA Curves.

稀土-铁石榴石的共价极化行为对光谱和穆斯堡尔谱的影响

利用平均能带模型研究了稀土 铁石榴石晶体化学键的性质 ,结果表明 ,这些晶体虽然包含的稀土离子不同 ,但计算得到的化学键参数值几乎相同。在每个化合物当中 ,金属离子与氧配体之间共价性随着Ln3+ (2 4c)、Fe3+ (16a)、Fc3+ (16d)的次序而增大。利用由共价性和极化率定义的化学环境因子h计算YIG中Fe3+ 的拉卡参数与实验值一致。建立了穆斯堡尔同质异能位移与h值的线性关系 ,讨论了居里温度与h值的相关性。

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

人造翡翠晶化区的研究

本文在１．１～５．５ＧＰａ压力、７５０～２０５０℃温度范围内通过对产物的ＸＲＤ分析得到了以非晶为原料时，纯硬玉翡翠ＮａＡｌＳｉ２Ｏ６和透辉石翡翠０．６ＮａＡｌＳｉ２Ｏ６－０．４ＣａＭｇＳｉ２Ｏ６的晶化区．经过对晶化区中不同Ｐ、Ｔ点产物的结晶度计算，将区域分成三个晶化子区，并对各子区中合成样品的硬度、微观结构、强度、颜色、透明性和稳定性等进行了研究．结果表明，在较高温度和压力的Ａ区产物具有高的结晶度、粗壮的线状微晶及高有序度的编织结构，对应着产物的高硬度、纯正的颜色及良好的透明度和稳定性，是宝石级翡翠的合成区.

多相氧载体CoO-MgO的ESR研究

用ESR方法研究了CoO-MgO固溶体作为多相氧载体的可逆吸氧性质。发现CoO-MgO表面的Co~(2+)可以以两种方式与分子氧可逆结合,一种形成Co~(2+)-O_2,它给出了与MgO晶格中Co~(2+)相似的各向同性的信号(g=4.2);一种形成Co~(2+)-O_2~-,它给出轴对称的信号(g_‖=2.141,A_‖=30G,g_⊥_=1.980,A_⊥=15G)。我们认为Co~(2+)-O_2是表面Co_(5c)~(2+)与O_2结合产生的,而Co~(3+)-O_2~-是由表面Co_(4c)~(2+)或Co_(3c)~(2+)与O_2结合形成的。

栽培燕麦和野燕麦C-带核型比较

对1个六倍体栽培燕麦(A.sativa)健壮燕麦和3个六倍体野燕麦(A.fatua)通北燕麦、五台燕麦和日本燕麦进行了C-带核型比较,结果表明,栽培燕麦与野燕麦C-带带型基本相似,但同时在多个染色体上不同材料间又有C-带多态性存在,多态性C-带显现在1C,4C,5C,8,10,13,15,19,20号染色体上.此研究结果可为这些种质资源在燕麦遗传育种中的研究和利用提供细胞学依据.

反射地震转换波成像方法研究

Multi-waves and multi-component get more and more attentions from oil industry. On the basis of existent research results, My research focuses on some key steps of OBC 4C datum processing. OBC datum must be preprocessed quite well for getting a good image. We show a flow chart of preprocess including attenuation of noise on multi-component datum、elimination ghost by summing P and Z and rotation of horizontal components. This is a good foundation for the coming steps about OBC processing. How to get exact converted point location and to analyze velocity are key points in processing reflection seismic converted wave data. This paper includes computing converted point location, analyzing velocity and nonhyperbolic moveout about converted waves. Anisotropic affects deeply the location of converted wave and the nonhyperbolic moveout. Supposed VTI, we research anisotropic effect on converted wave location and the moveout. Since Vp/Vs is important, we research the compute method of Vp/Vs from post-stack data and pre-stack data. It is a part of the paper that inversing anisotropic parameter by traveltime. Pre-stack time migration of converted wave is an focus, using common-offset Kirchhoff migration, we research the velocity model updating in anisotropic media. I have achieved the following results: 1) using continued Fractions, we proposed a new converted point approximate equation, when the offset is long enough ,the thomsen’s 2 order equation can’t approximate to the exact location of converted point, our equation is a good approximate for the exact location. 2) our new methods about scanning nonhyperbolic velocity and Vp/Vs can get a high quality energy spectrum. And the new moveout can fit the middle and long offset events. Processing the field data get a good result. 3) a new moveout equation, which have the same form as Alkhalifah’s long offset P wave moveout equation, have the same degree preciseness as thomsen’s moveout equation by testing model data. 4) using c as a function of the ratio offset to depth, we can uniform the Li’s and thomsen’s moveout equation in a same equation, the model test tell us choice the reasonable function C can improve the exact degree of Li’s and thomsen’s equation. 5) using traveltime inversion ,we can get anisotropic parameter, which can help to flat the large offset event and propose a model of anisotropic parameter which will useful for converted wave pre-stack time migration in anisotropic media. 6）using our pre-stack time migration method and flow, we can update the velocity model and anisotropic parameter model then get good image. Key words: OBC, Common converted Point (CCP), Nonhyperbolic moveout equation, Normal moveout correction, Velocity analysis, Anisotropic parameters inversion, Kirchhoff anisotropic pre-stack time migration, migration velocity model updating