稀土添加剂对高分子铑配合物催化甲醇羰基基化反应的促进作用

稀土添加剂对高分子铑配合物催化甲醇羰基基化反应的促进作用彭文庆，袁国卿（中国科学院化学研究所北京１０００８０）关键词甲醇，添加剂，羰基化稀土金属化合物作为催化剂的研究，由于其在某些反应中具有比过渡金属更优良的性能，引起了人们的普遍重视。对于甲醇羰基化...     

载体对醇气相羰基化镍催化剂的影响

载体对醇气相羰基化镍催化剂的影响彭峰冯景贤黄仲涛（华南理工大学化工学院化工系，广州５１０６４１）关键词催化剂，羰基化，载体，相互作用甲醇、乙醇的气相羰基化近二十年来引起了许多研究者的关注，在寻找一种廉价高效的非贵金属取代铑催化剂方面已取得了一定进展...     

多相高分子镍配合物催化甲醇羰基化反应研究

制备了2-乙烯基吡啶/丙烯酸乙二醇酯交联球型共聚物为配体,与氯化镍形成的高分子镍配合物.该配合物比表面积为70～85 m2/g,在反应介质中具有较好的溶胀性.在对配合物进行表征的基础上,对该催化剂催化甲醇羰基化制备醋酸的性能与反应条件的关系进行了研究.结果表明,该配合物催化甲醇羰基化反应具有较好的活性和选择性.     

添加稀土氯化物对甲醇低压气相羰基化制备醋酸的影响

将适量稀土添加到镍基催化剂中，并用BET、XRD和TPR对催化剂进行了表征， Ni-La/AC系列催化剂用于甲醇低压气相羰基化的结果表明，稀土（主要成分为LaCl3）对羰基化反应的诱导期、甲醇转化率和羰基化产物的收率产生了有利的影响，Ni（5%）-La （3.8%）/AC表现出较好的催化活性，比单金属负载Ni/AC催化剂在相同条件下，转化率提高了11.52%，羰基化主产物总收率提高了12.16%。     

甲醇气相法羰基化合成乙酸的镍催化剂(YhNi)的研究

本文报导了一种新型的甲醇羰基化生产乙酸的镍催化剂.由于选用了由聚偏二氯乙烯热裂解制得的特殊碳化物为载体,所以该催化剂有大比表面积,孔径分布均匀,并有优良的热稳定性和机械强度,其催化甲醇羰基化的速率在相对温和的条件下达到582克乙酸/克镍/时,高于文献报导的镍金属催化剂.     

高分子铑配合物（PYBRh）催化甲醇羰基化为乙酸和乙酸酐的动力学研究

采用２－乙烯吡啶－丁烯酮共聚物为配体，与四羰基二氯二铑形成顺二羰基铑（Ｉ）配合物（ＰＹＢＲｈ），用于催化甲醇羰基化制备乙酸和乙酸酐的反应动力学研究。结果表明，其对反应物甲醇和一氧化碳均为零级反应，在一定范围内，对高分子铑催化剂及助催化剂碘甲烷均为一级反应，极性溶剂的加入可以提高甲醇羰基化速度。通过实验结果计算了其反应活化能，活化熵和热焓研究证明其反应机理与小分子铑催化剂相似。     

甲醇气相羰基化制备乙酸的钴催化剂(YSCo)的研究

甲醇气相羰基化制备乙酸的钴催化剂（ＹＳＣｏ）的研究潘平来，柳忠阳，黄茂开，袁国卿（中国科学院化学研究所，北京１０００８０）关键词甲醇，羰基化，乙酸，钴催化剂通过甲醇羰基化制备乙酸是目前乙酸工业最先进的技术路线．该法与乙烯和乙醇氧化法相比较，无论从原料...     

螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨

螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨潘平来，柳忠阳，王晓筠，黄茂开，袁国卿（中国科学院化学研究所，北京１０００８０）１引言甲醇在铑催化剂的作用下，与一氧化碳反应羰基化为乙酸，是一个重要的基本有机合成，反应。在为数众多的催化剂中，锗的配合物...     

甲醇碳基化制乙酸

Monsanto公司的甲醇羰基化制乙酸工艺具有甲醇转化率高、产物产率高等优点，但也存在着主催化剂铑价格昂贵、助催化剂碘化物腐蚀设备等缺点。本文重点从催化机理研究方面介绍了国内外对Monsanto技术的最新改进研究工作、英国石油(BP)公司的甲醇羰基化制乙酸铱基催化体系(名为Cativa^TM工艺)，并介绍了无碘化物促进的甲醇羰基化催化体系，分析了不同催化体系的优缺点及研究发展趋势。     

甲醇羰基化的高分子催化剂（PVMRh）的稳定性研究

研究了以交联共聚物（ＰＶＭ）大孔隙树脂为配体的羰基铑配合物的热稳定性和抗空气氧化稳定性．这种类型的高分子铑催化剂不仅比类似的小分子铑配合物在甲醇羰基化反应中有着明显的高活性，而且在稳定性方面亦有着小分子配合物不可比拟的特点。实验结果表明，这类高分子催化剂在空气中的稳定温度达到１７０℃。在空气中室温放置５万小时后，其催化剂仍能保持不变。     

聚烯丙硫醇/丙烯酸甲酯羰基铑(Ⅰ)配合物的分子内取代反应

合成了一种新的含有S、O未配位原子的高分子顺二羰基铑配合物 ,用IR和XPS数据研究了其分子内羰基取代反应 ,结果表明在遇热且无CO保护下S、O与铑形成的弱的S→Rh、O→Rh键可取代强的Rh→Cπ键 ,形成稳定的四配位结构 ,从而保护了铑不因末端羰基脱落而分解 ,提高了它的稳定性 ;其分子内取代反应是可逆的 ,在CO气氛下该结构又能够回复到二配位结构     

制备因素对Ni—Co—O复合氧化物结构及氧化活性的影响

用共沉淀法和机械混合锻烧法制备了Ｎｉ－Ｃｏ－Ｏ复合氧化物催化剂。用ＴＰＲ、ＸＲＤ氧化活性评价等实验手段对催化剂进行了考察。结果表明不同方法制得的复合氧化物呈现不同的催化行为。共沉淀的ｐＨ值的高低及焙烧温度对催化剂的氧化活有较大影响，尖晶石型复合相ＮｉＣｏ２Ｏ４可能是提高催化剂氧活性的活性相。     

Synthesis, crystal structure, spectroscopic, magnetic, theoretical, and microbiological studies of a nickel(II) complex of L-tyrosine and imidazole, [Ni(Im)2(L-tyr)2]·4H2O

The [Ni(Im)(2)(L-tyr)(2)]·4H(2)O (1) complex was obtained in crystalline form as a product of interaction of L-tyrosine sodium salt, imidazole, and NiSO(4). The X-ray structure was determined, and the spectral (IR, FIR, NIR-vis-UV, HF EPR) and magnetic properties were studied. The Ni(2+) ion is hexacoordinated by the N and O atoms from two L-tyrosine molecules and by two N atoms of imidazole, resulting in a slightly distorted octahedral [NiN(2)N(2)'O(2)] geometry with a tetragonality parameter T = 0.995. The bands observed in the electronic spectra were ascribed to the six spin-allowed electronic transitions (3)B(1g) → (3)E(g) and (3)B(2g), (3)B(1g) → (3)A(2g) and (3)E(g), and (3)B(1g) → (3)A(2g) and (3)E(g). The spin Hamiltonian parameters g, D, and E, which were determined from high-field HF EPR spectra, excellently reproduced the magnetic properties of the complex. Calculation of the zero-field splitting in the S = 1 state of nickel(II) using DFT and UHF was attempted. The biological activity of the complexes has been tested for antifungal and antibacterial effects against Aspergillus flavus, Fusarium solani, Penicillium verrucosu, Bacillus subtilis, Serratia marcescens, Pseudomonas fluorescens, and Escherichia coli.     

Silylene–Nickel Promoted Cleavage of B−O Bonds: From Catechol Borane to the Hydroborylene Ligand

The first 16 valence electron [bis(NHC)](silylene)Ni⁰ complex 1 , [(^TMSL)ClSi:→Ni(NHC)₂], bearing the acyclic amido-chlorosilylene (^TMSL)ClSi: (^TMSL=N(SiMe₃)Dipp; Dipp=2,6-Prⁱ₂C₆H₄) and two NHC ligands (N-heterocyclic carbene=:C[(Prⁱ)NC(Me)]₂) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi-NiH complex 2 . Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene-coordinated (chloro)(silyl)nickel(II) complex 3 , {[cat(^TMSL)Si](Cl)Ni←:BH(NHC)₂}, via the cleavage of two B−O bonds and simultaneous formation of two Si−O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B−O bonds.     

Synthesis of a Metallo‐Iminosilane via a Silanone–Metal π‐Complex

Facile oxygenation of the acyclic amido‐chlorosilylene bis(N‐heterocyclic carbene) Ni⁰ complex [{N(Dipp)(SiMe₃)ClSi:→Ni(NHC)₂] ( 1 ; Dipp=2,6‐ⁱPr₂C₆H₄; N‐heterocyclic carbene=C[(ⁱPr)NC(Me)]₂) with N₂O furnishes the first Si‐metalated iminosilane, [DippN=Si(OSiMe₃)Ni(Cl)(NHC)₂] ( 3 ), in a rearrangement cascade. Markedly, the formation of 3 proceeds via the silanone (Si=O)–Ni π‐complex 2 as the initial product, which was predicted by DFT calculations and observed spectroscopically. The Si=O and Si=N moieties in 2 and 3 , respectively, show remarkable hydroboration reactivity towards H−B bonds of boranes, in the former case corroborating the proposed formation of a (Si=O)–Ni π‐complex at low temperature.     

Silylene–Nickel Promoted Cleavage of B−O Bonds: From Catechol Borane to the Hydroborylene Ligand

The first 16 valence electron [bis(NHC)](silylene)Ni⁰ complex 1 , [(^TMSL)ClSi:→Ni(NHC)₂], bearing the acyclic amido‐chlorosilylene (^TMSL)ClSi: (^TMSL=N(SiMe₃)Dipp; Dipp=2,6‐Prⁱ₂C₆H₄) and two NHC ligands (N‐heterocyclic carbene=:C[(Prⁱ)NC(Me)]₂) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi‐NiH complex 2 . Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene‐coordinated (chloro)(silyl)nickel(II) complex 3 , {[cat(^TMSL)Si](Cl)Ni←:BH(NHC)₂}, via the cleavage of two B−O bonds and simultaneous formation of two Si−O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B−O bonds.     

用EXAFS研究NiO在γ-Al2O3表面上的分散

本文使用EXAFS方法研究NiO在γ-Al_2O_3的表面上的分散情况。文章讨论了Ni含量为7%、13%、18%、26%、35%的NiO/γ-Al_2O_3体系的径向结构函数图以及Ni含量为13%、26%的NiO/α-Al_2O_3样品的径向结构函数图,认为NiO能在γ-Al_2O_3表面上成单层分散。分散后的Ni-O距离接近NiO晶体的Ni-O距离,表明Ni离子和γ-Al_2O_3表面上的氧有很强的相互作用。     

A computational study on the intriguing mechanisms of the gas-phase thermal activation of methane by bare [Ni(H)(OH)]+

A detailed computational study on the reaction mechanisms of the thermal activation of methane by the bare complex [Ni(H)(OH)](+) has been conducted. The experimentally observed reaction features, i.e. the ligand exchange Ni(H) → Ni(CH(3)), the H/D scrambling between the incoming methane and the hydrido ligand of the nickel complex, the spectator-like behavior of the OH ligand, and the relatively moderate reaction efficiency of 6% relative to the collision rate of the ion/molecule reaction, can be explained by considering three competing mechanisms, and a satisfactory agreement between experiment and theory has been found.     

钯丙烯酸酯络合物的~(13)C NMR谱的研究

用~(13)C NMR、~(31)P NMR谱研究了络合物Pd(mma,)(PMePh_2)_2(Ⅰ)、Pd(ema)(PMePh_2)_2(Ⅱ)中金属与mma、ema间配位状态及溶液中的动态行为。对比了相同配体的Pd、Ni络合物中烯基碳化学位移的变化,研究了中心金属电子反馈能力与络合物稳定性的关系。     

Ga2O3-NiO复合氧化物的溶胶-凝胶法制备和气敏性能

用溶胶-凝胶法制备了Ga2O3-NiO复合金属氧化物气敏材料,对其相组成、电导和气敏性能作了研究.结果表明:镍镓物质的量比n(Ni2＋) : n(Ga3＋)=0.7～0.9:2、800 ℃下热处理4 h,得到纯相尖晶石型复合金属氧化物NiGa2O4.缺陷GaNi×的反应(GaNi×→GaNi’＋h●),使NiGa2O4呈p型半导体. n(Ni2＋) : n(Ga3＋)=1:2凝胶粉在800 ℃下热处理4 h,所得纳米微粉制作的元件在313 ℃工作温度下对C2H5OH有较高灵敏度和良好的选择性.