A Comparison of the Stability and Reactivity of Diamido‐ and Diaminocarbene Copper Alkoxide and Hydride Complexes

The mononuclear N‐heterocyclic carbene (NHC) copper alkoxide complexes [(6‐NHC)CuOtBu] (6‐NHC=6‐MesDAC ( 1 ), 6‐Mes ( 2 )) have been prepared by addition of the free carbenes to the tetrameric tert‐butoxide precursor [Cu(OtBu)]₄, or by protonolysis of [(6‐NHC)CuMes] (6‐NHC=6‐MesDAC ( 3 ), 6‐Mes ( 4 )) with tBuOH. In contrast to the relatively stable diaminocarbene complex 2 , the diamidocarbene derivative 1 proved susceptible to both thermal and hydrolytic ring‐opening reactions, the latter affording [(6‐MesDAC)Cu(OC(O)CMe₂C(O)N(H)Mes)(CNMes)] ( 6 ). The intermediacy of [(6‐MesDAC)Cu(OH)] in this reaction was supported by the generation of Cu₂O as an additional product. Attempts to generate an isolable copper hydride complex of the type [(6‐MesDAC)CuH] by reaction of 1 with Et₃SiH resulted instead in migratory insertion to generate [(6‐MesDAC‐H)Cu(P(p‐tolyl)₃)] ( 9 ) upon trapping by P(p‐tolyl)₃. Migratory insertion was also observed during attempts to prepare [(6‐Mes)CuH], with [(6‐Mes‐H)Cu(6‐Mes)] ( 10 ) isolated, following a reaction that was significantly slower than in the 6‐MesDAC case. The longer lifetime of [(6‐Mes)CuH] allowed it to be trapped stoichiometrically by alkyne, and also employed in the catalytic semi‐reduction of alkynes and hydrosilylation of ketones.     

醇钾及酚钾在甲基丙烯酸甲酯阴离子聚合中的应用

以正丁基锂(n-BuLi)为引发剂,叔丁醇钾(t-BuOK)和苯酚钾(POK)为副反应抑制剂,实现了甲基丙烯酸甲酯(MMA)在四氢呋喃(THF)溶剂中的阴离子聚合。采用凝胶渗透色谱(GPC)、核磁共振氢谱(1 H-NMR)等研究了产物的数均分子量、分子量分布(MWD)和分子结构。结果表明:t-BuOK与n-BuLi之间发生反离子交换反应使活性中心的反离子Li~+被K~+替换,从而在一定程度上抑制了MMA聚合过程中的副反应,当n(t-BuOK)/n(n-BuLi)≥10时,可在0℃下实现MMA的可控阴离子聚合;PMMA分子量分布较窄(1.22),且数均分子量与设计值十分接近,MMA聚合的副反应得到了有效控制;进一步添加的POK能与活性中心的K~+配合,促进对MMA聚合副反应的抑制,使MMA的可控阴离子聚合能在较高温度(40℃)下得以实现,所合成的聚甲基丙烯酸甲酯(PMMA)数均分子量分布窄(1.24)且数均分子量符合设计值。     

Influence of Preparation Conditions on Crystallization Behavior of the Complex Alkoxide Derived PbTiO3 Powder

PbTiO₃ powders were prepared by hydrolysis of the complex alkoxide derived from Pb(OCOCH₃)₂ and Ti(OCH₂CH₃)₄, and their crystallization behaviors were investigated by DTA. Influence of conditions of synthesis and hydrolysis of the Pb-Ti complex alkoxide and heating atmosphere on crystallization behavior of powder was examined.Powders consisting of spherical particles with submicron diameter could be obtained by using the reaction time over 16 hr for synthesis, and the use of acetone-ethanol solvent with ammonia catalyst for the hydrolysis of the complex alkoxide. The resultant powders crystallized to tetragonal PbTiO₃ perovskite above 250°C under O₂ flow, and then transformed to cubic perovskite at 490°C. The powder heated at 250°C for 1 hr in O₂ consisted of well-crystallized tetragonal perovskite crystals of cubic shape of 0.2 to 1 µm in size.     

醇盐水解法制备钛酸铅微粉的机理研究

采用ＴＧ－ＤＴＡ、ＸＲＤ、ＩＲ等手段研究了醇盐水解法制备的钛酸铅微粉的晶化行为，并用化学分析方法对微粉中可溶铅含量做了研究。结果表明，未昌化微粉中Ｐｂ以无定形ＰｂＴｉＯ３和无定形ＰｂＯ两种形式存在，当热处理温度达到晶化温度区间（４３０￣４７０℃）时，无定形ＰｂＴｉＯ３向结晶型ＰｂＴｉＯ３的转化和无定形ＰｂＯ与ＴｉＯ２间的反应同时发生。     

Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare‐Earth Complexes: Non‐Redox Oxygen Atom Transfer

The preferential substitution of oxo ligands over alkyl ones of rare‐earth complexes is commonly considered as “impossible” due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare‐earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln‐oxo bond, but also protect the highly reactive Ln‐alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non‐redox rare‐earth‐mediated oxygen atom transfer from ketones to CS₂ and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare‐earth oxo complexes.     

Synthesis,Reactivity and Antimicrobial Activity of a Series of 2-Arylamino-1,3-selenazoles

A series of 2-arylamino-1,3-selenazoles was synthesized and their reactivity was studied. The 2-arylamino-1,3-selenazoles and their reaction products were characterized by various spectroscopic methods and X-ray diffraction. In addition, the antimicrobial activity of the 2-arylamino-1,3-selenazoles in a panel of seven bacteria and fungi was examined.     

混合配体构筑的配位聚合物的合成、结构与荧光性质

在溶剂热条件下,利用Cd(Ⅱ)、Co(Ⅱ)在混配体体系下合成出3个结构新颖的配位聚合物[Cd_3(pic)_4(H_2bmimb)]n(1),[Co_3(pic)4(H_2bmimb)]n(2)和[Cd_2(1,2-mbix)(pic)_2(H_2O)_2]_n(3)(pic=5-苯基间苯二甲酸;H_2bmimb=1,4-二((2-甲基咪唑)亚甲基)苯;1,2-mbix=1,2-二((2-甲基咪唑)亚甲基)苯),并通过单晶X射线衍射、红外光谱、热重分析、元素分析、粉末X射线衍射和荧光光谱等对配合物进行了表征。配合物1和2中金属离子Cd~(2+)、Co~(2+)均与pic配体形成了三维阴离子骨架,双质子化的双咪唑配体位于骨架中平衡骨架电荷。配合物3中,Cd~(2+)金属中心与pic、1,2-mbix配体配位形成一维链,链与链之间通过苯环间的π…π堆积形成二维层,进而通过氢键形成三维超分子结构。配合物1和3表现出良好的荧光性质。     

纳米nah高化学反应活性

纳米氢化钠;氯苯氢解;肉桂醛选择还原;二甲亚砜金属取代反应;烯烃催化加氢     

Enantioselective total synthesis of (R)-strongylodiols A and B

We describe an expeditious enantioselective total synthesis of the acetylenic marine natural products (R)-strongylodiols A and B. Central to the strategy is the use of Zn(OTf)₂, amine base, and N-methyl ephedrine to mediate the direct addition of a 1,3-diyne to two long-chain aliphatic aldehydes in useful selectivities and yields.     

Effect of the Alkali-Metal Cations On the Protonation Constants of Myo-Inositol Hexakis(Phosphate)

Abstract

Values for the protonation constants of myo-inositol hexakis(phosphate) have been determined at 25°C and 0.1 M ionic strength by potentiometry in media containing two different concentrations of Li⁺, Na⁺, K⁺ and Cs⁺ salts.

The Alog K_yHM values, which correspond to the differences between the constants obtained with and without alkali-metal cations, are considered as being related to the binding ability of the ligand towards these cations.

Their relative behaviour is then analysed and some conclusions are drawn about the conformations which might be adopted by the complexes in different pH regions.     

An unusual behaviour of N-(tert-butoxycarbonyl)- and N-pivaloyl-(methylthio)anilines in metallation reactions

The metallation reaction of N-Boc-and N-Piv-(methylthio)anilines are here described. The results show that N-Boc derivatives are metallated only by superbases to give products substituted at the thiomethylic group. N-Piv derivatives show a different behaviour: ortho-derivative is metallated by both butyllithium and superbase at the thiomethylic carbon atom, while para-derivative is metallated in ortho to the N-Piv group by butyllithium and at the thiomethylic carbon atom by superbase. The meta-derivative is metallated only by superbase at the thiomethylic carbon atom.     

Sol-Gel Synthesis of Nano-Scaled BaTiO3, BaZrO3 and BaTi0.5Zr0.5O3 Oxides via Single-Source Alkoxide Precursors and Semi-Alkoxide Routes

Sol-gel synthesis of nano-sized BaTiO₃, BaZrO₃ and BaTi_0.5Zr_0.5O₃ ceramics using alkoxide and semi-alkoxide routes has been investigated and the pervoskites obtained have been compared with respect to crystallisation temperature, crystallite size and compositional purity. Heterometal alkoxides containing two (for BaTiO₃ and BaZrO₃) and three (for BaTi_0.5Zr_0.5O₃) different metals were used as single-source precursors in the alkoxide route while semi-alkoxide synthesis was performed by reacting barium hydroxide or acetate with Ti and/or Zr alkoxides. Semi-alkoxide synthesis also produces stoichiometric and phase-pure oxides, however, at temperatures higher than 1000°C. At temperatures below 1000°C, BaCO₃ and small amounts of other undesired phases (e.g., BaTi₂O₄) were present in the oxides derived from semi-alkoxide synthesis. Thermal behaviour, studied by TGA/DTA measurements, shows that thermal decomposition occurs in three major steps and depends on the educt composition and the synthesis route. Among alkoxide derived powders, crystalline BaTi_0.5Zr_0.5O₃ phase is formed at 400°C while complete crystallisation of BaMO₃ ceramics occurs around 600°C. The cubic to tetragonal phase transition for BaTiO₃ is clearly observed at relatively low-temperature of 800°C. The stoichiometry and phase homogeneity of the obtained powders were demonstrated by energy dispersive X-ray analysis and powder diffractometry. The averaged crystallite size of the obtained nano-ceramics was evaluated using the FormFit programme. SEM and TEM observations revealed a high microstructural uniformity.     

色谱质谱联用技术研究30%二甲基二乙氧基硅烷/70%正硅酸乙酯复合醇盐的水解聚合行为

采用色谱质谱联用技术研究了1种复合醇盐：30％二甲基二乙氧基硅烷／70％正硅酸乙酯（DDS／TEOS）的水解聚合过程，并由此分析了这两种有机-无机酸盐的相互作用机制和聚合方式，实验结果指出，DDS的添加抑制了TEOS的自聚合，使得体系中形成了大量的DDS的自聚合环状分子（（（CH3）2Si—O—）n）以及TEOS和DDS的共聚合高分子，由于后者对水解聚合的加速作用，使得30％DDS／70％TEOS系统具有最短的凝胶时间。     

Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses,Structures, Reactivity,and Catalysis

A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L^?=Ph₂PNDip^?, Dip=2,6‐diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)₄] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ‐bond metathesis catalytic cycle of an in situ formed “MgH₂” active species.     

Preparation and Properties of Nb-Coated Barium Titanate Composite Particles by Surface Modification with Nb Alkoxide in Hydrophobic Solvent

Chemical processing for the preparation of Nb-coated barium titanate composite particles was investigated using surface modification technology, hydrolyzing Nb ethoxide on the surface of barium titanate particles dispersed in hydrophobic solvent.It was confirmed from the measurements of specific surface area and zeta potential as well as SEM, TEM and EDX observations of the resulting composite particles that the original barium titanate particles were coated uniformly with hydrolysis product of Nb ethoxide.Barium titanates coated with 1 wt% of Nb as oxide were well sintered at 1200–1300°C. The dielectric constants of the sintered barium titanates showed flattened temperature dependence, but it depended upon the average particle size of original barium titanate. The sintered bodies of Nb-coated barium titanate powders with average particle size of 0.2 m gave dielectric constants of 2000–3000 and those of barium titanate with average particle size of 0.5 m showed dielectric constants of 3000–4000 at room temperature.The microstructure of the sintered barium titanate coated with Nb oxide consisted of grains of about 1 m, smaller than those of sintered original barium titanate.     

Interconverting WW Triple Bonds and W4 Clusters: Structures of W4(OPrn)16 and [Li2W2(OPrn)8(DME)]2*

Alcoholysis of W₂(NMe₂)₆ with excess n-propanol in hexane yields the tetranuclear cluster, W₄(OPrⁿ, I. Reduction of I with two equivalents of Li₂COT in THF gives a small yield of Li₂W₂(OPrⁿ)₈. Single crystals were isolated by cooling the product mixture in DME and were shown to be [Li₂W₂(OPrⁿ)₈(DME)]₂, II, which consists of a unique “dimer of dimers” structure. In this reaction sequence, W₄¹⁶⁺ cluster formation is followed by four electron reduction to reform the (W≡W)⁶⁺ unit. Better yields of the lithium salt can be obtained by the addition of LiOPrⁿ/HOPrⁿ solutions to W₂(OBu^t)₆ in which case Li₂W₂(OPrⁿ)₈ has been obtained as a 1:1 adduct with LiOPr. This identity of this salt was confirmed by solution NMR spectroscopy. In the alternative reaction, the (W≡W)⁶⁺ center remains intact from reactant to product. No attempt has been made to separate the product from excess LiOPr. DFT (ADF 2004.01) molecular orbital calculations on the model cluster W₄(OH)₁₆ are used to help elucidate the disruption of the W₄ cluster upon four electron reduction. The molecular structures of compounds I and II are reported.*Dedicated to Professor F. A Cotton on the occasion of his 75th birthday.     

Metallation of fullerenes: electrochemical synthesis and voltammetric study of heterometallic C60 and C70 complexes

Electrochemical synthesis and voltammetric study of new heterotrimetallic exohedral derivatives of [60]- and [70]fullerenes containing palladium and manganese atoms were carried out. The MO involved in redox transitions were determined by the semiempirical quantum-chemical calculations and by the comparison of the potentials for the redox transitions of the heterotrimetallic complexes and their fullerene and metal-containing fragments.     

Reductive lithiation of alkyl phenyl sulfides in diethyl ether. A ready access to α,α-dialkylbenzyllithiums

Diethyl ether is a convenient solvent for the conversion of benzylic phenyl sulfides to the corresponding organolithiums by an uncatalyzed reductive metalation, while catalysis by naphthalene is required to achieve the same reaction for alkyl phenyl sulfides. The addition of magnesium 2-ethoxyethoxide to solutions of unstable alkyllithiums prepared in this way provides storable reagents.     

The ligand effect in Ti‐mediated living radical styrene polymerizations initiated by epoxide radical ring opening. 1. Alkoxide and bisketonate Ti complexes

Bisketonate and alkoxide Ti(III) complexes derived from Zn reduction of Ti(IV) precursors were evaluated as catalysts for the living radical polymerization (LRP) of styrene initiated by Ti‐catalyzed epoxide radical ring opening and mediated by reversible termination with Ti(III). No polymerization occurred with tris(2,2,6, 6‐tetramethyl‐3,5‐heptanedionato)titanium (III), whereas dichlorobis(2,2,6,6‐tetramethyl‐3,5‐heptanedionato)titanium (IV) affords only a free radical polymerization. Preliminary living features were displayed by (ⁱPrO)₂TiCl₂. Investigations of the effect of epoxide/Ti/Zn ratios, temperature, and nature of the epoxide demonstrated that (ⁱPrO)₃TiCl provides a linear dependence of M_n on conversion over a wide range of conditions with an optimum for [Sty]/[epoxide group]/[Ti]/[Zn] = 50/1/2/4 at 90 °C. However, the polydispersity could not be reduced below 1.4–1.5, with an initiator efficiency of 0.15. These results were rationalized in terms of a combination of decreased Ti oxophilicity and ligand exchange. The lowered oxophilicity decreases the initiation rate and broadens M_w/M_n. The fast alkoxide exchange promotes a weak dependence of the polymerization on reaction conditions and generates macromolecular Ti species with reduced ability to mediate LRP. Thus, while monofunctional epoxides provide homogeneous polymerizations and narrower M_w/M_n, difunctional initiators may lead to gel formation at high conversion. Nonetheless, all polymerizations were light gray to colorless and afforded white polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6028–6038, 2005