Rh2（CO）4（μ—Cl）2 和Rh4（μ—CO）3（CO）9的简正振动分析

金属簇合物因其独特的结构和成键而引人注目，鉴于文献上对铑簇合物的结构、成键、反应和催化性能存在的不同看法，本文的两个铑簇合物的简正振动分析以及另文的铑系簇合物的电子结构计算和催化性能研究，为进一步认识上述问题提供了有意义的结果。     

（dppe）Rh（μ—CO）2M（CO）3（M=Cr,Mo,W）的合成,表征和催化功能

合成和表征了（ｄｐｐｅ）（Ｒｈ（μ－ＣＯ）２Ｍ（ＣＯ３）（Ｍ＝Ｃｒ，Ｍｏ，Ｗ）异双核金属羰基化合物，考察了ＳｉＯ２负载的这组配合物催化一氧化碳氢化反应和丙烯氢甲酰化反应的活性和性，记录了催化生氧化碳氢化反应的原位ＦＴ－ＩＲ谱。     

STUDY ON REACTION OF （μ_3－CCO_2Et）CO_2M（CO）_8（CpMe）（M＝Mo，W） WITH Na_2［Fe（CO）_4］．SYNTHESIS OF TWO KINDS OF THE NOVEL CLUSTERS EtO_2CCFeCoM（CO）_8（CpMe）H AND （OCC）FeCoM（CO）_8（CpMe）

ＳＴＵＤＹＯＮＲＥＡＣＴＩＯＮＯＦ（μ_３－ＣＣＯ_２Ｅｔ）ＣＯ_２Ｍ（ＣＯ）_８（ＣｐＭｅ）（Ｍ＝Ｍｏ，Ｗ）ＷＩＴＨＮａ_２［Ｆｅ（ＣＯ）_４］．ＳＹＮＴＨＥＳＩＳＯＦＴＷＯＫＩＮＤＳＯＦＴＨＥＮＯＶＥＬＣＬＵＳＴＥＲＳＥｔＯ_２ＣＣＦｅＣｏＭ（ＣＯ）_８...     

A Convenient Synthesis and Properties of Ru（bpy）2[bpy（CO2H）-（CO2Et）]（PF6）2 Photosensitive Dye

A novel Ru(Ⅱ) tris-bipyridyl complex, Ru(bpy)2[bpy(CO2H)(CO2Et)][PF6]2 is prepared in a simple and convenient process. It will be an alternative of Ru(bpy)2bpy(CO2Et)2(PF6)2 to be used in solar cells as photosensitive dyes.     

（dppe）Rh（μ－CO）_2M（CO）_3（M＝Cr、Mo、W）的合成，表征和催化功能

合成和表征了（ｄｐｐｅ）Ｒｈ（μ－ＣＯ）２Ｍ（ＣＯ）３（Ｍ＝Ｃｒ、Ｍｏ、Ｗ）异双核金属羰基化合物。考察了ＳｉＯ２负载的这组配合物催化一氧化碳氢化反应和丙烯氢甲酰化反应的活性和选择性。记录了催化一氧化碳氢化反应的原位ＦＴ－ＩＲ谱     

Synthesis and Crystal Structure of （SiCl3）2Fe（CO）4

The compound （SiCl3）2Fe（CO）4 was synthesized and structurally characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2 1/n with α = 8.287（2）, b = 9.829（2）, c = 9.042（2） A, β = 96.19（3）°, V= 732.2（3） A^3, C4Cl6FeO4Si2, Mr = 436.77, Z = 2, Dc = 1.981 g/cm^3, F（000） = 424, μ（MoKα） = 2.282 mm^-1, the final R = 0.048 and wR = 0.164 for 1109 observed reflections （I 〉 2σ（I））. The crystal structure of （SiCl3）2Fe（CO）4 reveals that the Si（l）- Fe-Si（l）^a sequence is linear and perpendicular to the Fe（CO）4 cross-shaped plane.     

Infrared Photodissociation Spectroscopy of Ti＋（CO2）2Ar and Ti＋（CO2）n （n=3-7） Complexes

Ti＋（CO2）2Ar and Ti＋（CO2）n （n=3-7） complexes are produced by laser vaporization in a pulsed supersonic expansion. The ion complexes of interest are each mass-selected in a time- of-flight spectrometer, and studied with infrared photodissociation spectroscopy. For each complex, a sharp band in the CO stretching frequency region is observed, which confirms the formation of the OTi＋CO（CO2）~_l oxide-carbonyl species. Small OTi＋CO（CO2）~_1 complexes （n_〈5） exhibit CO stretching and antisymmetric CO2 stretching vibrational bands that are blue-shifted from those of free CO and CO2. The experimental observations indicate that the coordination number of CO and CO2 molecules around TiO＋ is five. Evidence is also observed for the presence of another electrostatic bonding Ti＋（CO2）2 structural isomer for the Ti＋（CO2）2Ar complex, which is characterized to have a bent OCO-Ti＋-OCO structure stabilized by argon coordination.     

（CH3）3NO存在下M（CO）5（M＋Fe,Ru,Os）的CO取代反应动力学研究

在(CH_3)_3NO存在下,PPh_3取代M(CO)_5(M=Fe,Ru,Os)中CO的反应速度遵循二级速度定律,分别与[M(CO)_5]和[(CH_3)_3NO]的一次方成正比,与[PPh_3]无关。反应速度按FeRu>Os的次序约减小4倍。 1 实验方法 典型的动力学实验中,将(CH_3)_3NO的C_2H_5OH溶液和PPh_3的己烷溶液分别用注射器加到体积合适的烧瓶中,再注入Fe(CO)_5并迅速震荡烧瓶,再取出一部分反应液立即注入充N_2     

SYNTHESES， CHARACTERIZATION AND CATALYSIS OF （dppe）Rh（μ－CO）_2M（CO）_3（M＝CR，Mo，W） CARBONYL COMPOUNDS

ＳＹＮＴＨＥＳＥＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ ＡＮＤ ＣＡＴＡＬＹＳＩＳ ＯＦ （ｄｐｐｅ）Ｒｈ（μ－ＣＯ）_２Ｍ（ＣＯ）_３（Ｍ＝ＣＲ，Ｍｏ，ｗ）ＣＡＲＢＯＮＹＬ ＣＯＭＰＯＵＮＤＳ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ；ＪａｉｅＹｕＷＡＮＧ；ＸｉｕＺ...     

担载Ru_3（CO）_（12）－Fe_2（CO）_9混合簇的脱羰基作用和表面加氢反应

担载于ＺｒＯ２上的Ｒｕ３（ＣＯ）１２－Ｆｅ（ＣＯ）９混合簇的红外光谱表明，Ｒｕ３（ＣＯ）１２以Ｒｕ（ＣＯ）２Ｏ２表面络合物存在．混合族在真空中随温度升高而发生脱羰基作用，５００℃左右羰基完全脱掉；以Ａｌ２Ｏ３为载体者其羰基不易脱除，升高温度出现多种羰基带．混合簇中的Ｆｅ２－（ＣＯ）９极易脱羰基．担载混合簇在Ａｒ气中进行ＴＰＤＥ时，低温时以脱羰基为主，高于１５０℃时发生表面歧化反应而生成ＣＯ２；在Ｈ２气中，低温时仍以脱羰基为主，高于１５０℃时发生表面加氢反应而生成ＣＨ４．混合簇的脱羰基和表面反应能力与Ｒｕ／Ｆｅ比及载体有关．担载混合簇在ＣＯ加氢反应中以Ｒｕ（ＣＯ）２Ｏ２和分散Ｆｅ存在，还出现－ＣＨｘ多种表面物种．     

Electrooxidation of CO on Ru（0001） and RuO2（ 100） Electrode Surfaces

The electrooxidation of CO on Ru(0001) and RuO2(100) electrode surfaces were characterized by cyclic voltammetry,AES and RHEED,The CO adlayer was first partially oxidized at 0.8 V, which is controlled by the attack of oxygen species toward the Ru(0001) surface. The remaining CO aldayer oxidation at 0.55 V is related to the combination of CO molecules with oxygen species already located on the surface,In contrast,successive peaks on RuO2(100) at 0.4 V and 0.72 V are observed ,which shows that CO molecules can directly react with two different lattice-oxygen on the surface to carbon dioxide.     

Synthesis and Reaction of [MnRe（CO）6（μ—SH）（μ—SC（H）PPr^i3）（PPh3）]

The synthesis,the crystal structure and the reaction of the hetero-binuclear complex[MnRe(CO)6(μ-SH）（μ-SC(H)PPr^i3)(PPh3)] are reported.The results of single crystal X-ray structure analysis showed that the fragments Mn(CO)3 and Re(CO)3 were bridged by SH and SC(H)PPr^i3.The title complexes can react with Bu^nLi and RX forming complexes MnRe(CO)6(μ-SR）（μ-SC(H)PPr^i3)(PPh3)](R=Me,CH2CH=CH2,SnBu3^n).     

The Effect of the CO（a~3П） Vibrational Population on the CO（a~3П）＋ NO（X~2П） Energy Transfer Reaction

ＴｈｅＥｆｆｅｃｔｏｆｔｈｅＣＯ（ａ~３П）ＶｉｂｒａｔｉｏｎａｌＰｏｐｕｌａｔｉｏｎｏｎｔｈｅＣＯ（ａ~３П）＋ＮＯ（Ｘ~２П）ＥｎｅｒｇｙＴｒａｎｓｆｅｒＲｅａｃｔｉｏｎＴｈｅＥｆｆｅｃｔｏｆｔｈｅＣＯ（ａ~３П）ＶｉｂｒａｔｉｏｎａｌＰｏｐｕｌａｔ...     

MOLECULAR AND CRYSTAL STRUCTURE OF （（C6H5）3P）2Ag（CO2H）

<正> C_37 H_31 O_2P_2Ag, Mr = 677. 47. The crystal structure belongs to mon-oclicnic system with space group Cc. Cell constants a =24. 952(2), b = 9. 179(1), c = 15. 262(1) A ,β= 116. 34 (2)°, V= 3132. 9 (3) A3, Z = 4, Dc = 1. 436g/cm3, D0 = 1. 43g/cm3.The final R achieved is 0. 052 for 5677 observed reflections, F (000) = 673. Like other silver complexes, Ag ( I ) in the center of the complex is 4-coordinat-ed. Formic acid anion also acts as a bidentate ligand in this complex beside two triph-enylphosphine groups.