芳基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=Ph (1),4-tolyl (2),4-chlorophenyl (3),4-methoxyphenyl (4),2-thienyl (5))分别与Ru₃(CO)₁₂在甲苯或二甲苯中加热回流,得到了5个双核配合物[(η⁵-C₉H₆R)Ru(CO)]₂(μ-CO)₂(R=Ph (6),4-tolyl (7),4-chlorophenyl (8),4-methoxyphenyl (9),2-thienyl (10))。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,7和10的结构。     

芳基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=Ph(1),4-tolyl(2),4-chlorophenyl(3),4-methoxyphenyl(1),2-thienyl(5))分别与Ru₃(CO)₁₂在甲苯或二甲苯中加热回流,得到了5个双核配合物[(η⁵-C₉H₆R)Ru(CO)]₂(μ-CO)₂(R=Ph(6),4-tolyl(7),4-chlorophenyl(8),4-methoxyphenyl(9),2-thienyl(10))。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,7和10的结构。     

烃基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=CH₂CH₂CH₃ (1),CH₂(CH₃)₂ (2),C₅H₉ (3),CH₂C₆H₅ (4),CH₂CH=CH₂ (5))分别与Ru₃(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η⁵-C₉H₆R)Ru(CO)(μ-CO)]₂(R=CH₂CH₂CH₃ (6),CH₂(CH₃)₂ (7),C₅H₈ (8),CH₂C₆H₅ (9),CH₂CH=CH₂ (10))和[(η⁵-C₉H₆)(H₃CH₂C)CHCH(CH₂CH₃)(η⁵-C₉H₆)] [Ru(CO)(μ-CO)]₂ (11).通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构.     

三态不饱和三核钌羰基化合物的理论研究

采用两种密度泛函方法和两种有效核势基组对中性不饱和三核钌羰基化合物Ru3(CO)n(n=11,10,9)的三态异构体进行理论计算,优化出8个稳定异构体.研究发现,三态异构体中带有多个非端羰基的异构体能量较低.对同一分子的三态异构体,所含非端羰基数目越多,则能量也越低.     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

新型膦胺配体羰基钌化合物的合成及其催化性能研究

以十二羰基三钌和o-PPh2C6H4NR2(R=H,Me)配体为原料,成功制备了三种新型羰基钌化合物(μ-o-PPh2-C6H4NH)Ru3(μ-H)(CO)9(2)、(o-PPh2C6H4NH)2Ru(CO)2(3)和(μ-o-PPh2C6H4NMe2)2Ru(CO)3(4).对这三个化合物进行了核磁共振和红外谱学、元素分析和X射线单晶衍射分析表征,并对这三个化合物进行了催化性能研究.化合物2和4可催化苯甲醛加氢反应生成苯甲醇,但是3没有催化活性.从实验角度阐述了膦胺配体钌催化剂的结构与性能关联,进一步探讨了加氢催化反应失活的可能原因.     

含硫帽的三核和四核钌羰基簇合物的合成和结构表征

The reaction of Ru₃(CO)₁₂ with five-membered cyclic SP(S)(Fc)N(Ph)NC(Me) gave two novel trinuclear and tetranuclear ruthenium carbonyl clusters containing capping S atoms in Ru₃(CO)₈(μ₃-S)₂[P(Fc)N(Ph)NC(Me)S] 1 and Ru₄(CO)₇(μ-CO)₃(μ₄-S)₂[P(Fc)N(Ph)NC(Me)S] 2 (Fc=C₅H₅FeC₅H₄). During the reaction, the ligand precursor cleaved only in its P=S bond to give the fragments S and [P(Fc)N(Ph)NC(Me)S], and then coordinated to the ruthenium atoms to form the clusters as listed above. The clusters have been characterized by elementary analysis, IR, ¹H NMR and MS spectroscopy. The crystal structure of cluster 2 has been determined by X-ary diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The unit cell parameters are as follows: a=1.18744(7) nm, b=1.36041(11) nm, c=2.20026(18) nm, β=104.126(3) °, V=3.4468(5) nm³, D_c=2.175 g·cm^-3, Z=4. In the molecule, the three bridging carbonyls and Ru4 are planar and with a pseudo-octahedral Ru₄S₂ skeleton. The terminal carbonyl of Ru1 was substituted by the cyclic ligand [P(Fc)N(Ph)NC(Me)S]. CCDC: 217076.     

取代四甲基环戊二烯基钌羰基化合物的合成及结构

将配体[C₅Me₄HR](R=cyclopentyl,cyclohexyl,ⁿPr)分别与Ru₃(CO)₁₂在二甲苯中加热回流,合成了3个新的双核配合物[(η⁵-C₅Me₄R)Ru(CO)(μ-CO)]₂(R=cyclopentyl(1),cyclohexyl(2),ⁿPr(3))。利用红外光谱、元素分析、核磁共振氢谱对它们的结构进行了表征,用X-射线单晶衍射法测定了1和2的结构。     

取代四甲基环戊二烯基钌羰基化合物的合成及结构

将配体[C5Me4HR](R=cyclopentyl,cyclohexyl,nPr)分别与Ru3(CO)12在二甲苯中加热回流,合成了3个新的双核配合物[(η5-C5Me4R)Ru(CO)(μ-CO)]2(R=cyclopentyl(1),cyclohexyl(2),nPr(3))。利用红外光谱、元素分析、核磁共振氢谱对它们的结构进行了表征,用X-射线单晶衍射法测定了1和2的结构。     

钌选择性催化烯丙醇无受体脱氢合成α,β-不饱和羰基化合物（英文）

过渡金属催化烯丙醇的选择性脱氢氧化以得到相应的α,β-不饱和羰基化合物在最近广受关注,但是很多方法需要用到化学计量的氧化剂,这会带来大量的废弃副产物,原子经济性不足.本工作开发了一种简单易得的[Ru Cl2(pcymene)]2催化系统,可用于高效地催化烯丙醇选择性脱氢合成α,β-不饱和羰基化合物,而无需使用额外的氧化剂或H2受体.     

A Modified Water-Gas Shift Reaction. The Decomposition of Alkyl Formate in the Presence of Water Using a Ruthenium Carbonyl

Alkyl formates in the presence of water were rapidly decomposed to H₂, CO₂ and the corresponding alcohols using Ru₃(CO)₁₂ and KOAc as catalyst. Based on the hydrogen gas produced, a turnover rate as fast as 8446/h for ethyl formate at 140°C was observed. The catalyst system was also active for the decomposition of other alkyl formates. The rate of decomposition increased both with increasing amount of KOAc and with decreasing number of carbon atom in the alkyl group of the formate. In addition to Ru₃(CO)₁₂, several other transition metal complexes RuCl₃, RuCl₂(PPh₃)₃, Os₃(CO)₁₂, H₂Os₃(CO)₁₀, RhCl₃, and RhCl(PPh₃)₃, were active in the catalytic decomposition of alkyl formates, although their activities varied greatly. The Ru₃(CO)₁₂-KOAc system also catalyzed the reduction of nitrobenzene by HCOOEt-H₂O to aniline in EtOH and to a mixture of N-phenylformamide and N-methyl-N-phenylformamide in HCOOEt. Under coditions the same as for the hydrogenation of nitrobenzene, ethylene styrene and cyclohexenone were reduced to the corresponding alkanes, whereas 1-hexene and 1-octene were isomerized to the corresponding 2-alkene products.     

羟甲基功能化吡唑金属羰基化合物的合成及催化性质

研究了3(5)-羟甲基-5(3)-甲基吡唑(L~1),4-羟甲基吡唑(L2)及双(3-羟甲基-5-甲基吡唑)甲烷(L3)与羰基钨(钼)的反应,合成了一系列以单齿及双齿氮配位的羰基金属衍生物LW(CO)5(L=L1或L2)和L3M(CO)4(M=Mo或W)。通过核磁、红外及X射线单晶衍射分析,对这些化合物进行了详细的结构表征。结果表明,这些化合物往往通过O-H…O,N-H…O及O-H…OC-M等氢键作用,形成一维或二维金属有机超分子结构。并且依赖于配体中羟甲基所处的不同位置,这些金属有机超分子表现出明显不同的结构特征。初步的催化活性测试表明,这些新化合物在苯乙炔三聚反应中具有明显的催化活性。     

Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds

The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp ( 1 ), (R,R)-Skewphos ( 2 ) and (S,S)-Skewphos ( 3 )) are easily obtained in 85–88 % yield through a one-pot synthesis from [RuCl₂(PPh₃)₃], the diphosphine and 2,2′:6′,2′′-terpyridine (tpy) in 1-butanol. Treatment of 1 – 3 with NaPF₆ in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF₆ (PP=dppp ( 1 a ), (R,R)-Skewphos ( 2 a ) and (S,S)-Skewphos ( 3 a )). Reaction of [RuCl₂(PPh₃)₃] with (S,R)-Josiphos or (R)-BINAP in toluene, followed by treatment with tpy in 1-butanol and finally with NaPF₆ in MeOH gives [RuCl(PP)(tpy)]PF₆ (PP=(S,R)-Josiphos ( 4 a ), (R)-BINAP ( 5 a )) isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a , 4 a have been characterized by single crystal X-ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2-propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h⁻¹. The chiral enantiomers 2 , 2 a and 3 , 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)- and (R)-1-phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2-propanol mixture.     

New Tetranuclear Ruthenium(I) Carbonyl Trifluoroacetate Complex: Gas-Phase Transformations and Coordination Reactions

A new mixed ligand ruthenium(I) complex of the composition [Ru₂(O₂CCF₃)₂(CO)₅] (1) has been prepared by refluxing Ru₃(CO)₁₂ with trifluoroacetic acid in a dichloromethane/benzene mixture. Crystals of 1 were obtained by gas phase sublimation of the crude product at 110°C. The X-ray diffraction study has revealed a tetranuclear `8dimer of dimers' 9 structure [Ru₂(O₂CCF₃)₂(CO)₅]₂ in 1. Complex 1 can be re-sublimed without decomposition at temperatures up to 130°C, while at higher temperatures fragmentation accompanied by a ligand re-distribution reaction has been observed. As a result, two new ruthenium(I) complexes have been isolated from the gas phase transformation of 1 at 160°C: [Ru₂(O₂CCF₃)₂(CO)₆] (2) and [Ru₂(O₂CCF₃)₂(CO)₄] (3). Complex 2 has a dinuclear cis-trifluoroacetato-bridged core, while 3 exhibits a polymeric structure built on axial Ru···O interactions of the dimetal units, [Ru₂(O₂CCF₃)₂(CO)₄]. The above reaction suggests the possible gas phase dissociation of the tetranuclear molecule 1 to the dimetal fragments, [Ru₂(O₂CCF₃)₂(CO)₅] that have one open axial coordination site. The latter was proved by codeposition of 1 with an aromatic hydrocarbon, [2. 2]paracyclophane, that afforded a new sandwich compound, [Ru₂(O₂CCF₃)₂(CO)₅·(₂-C₁₆H₁₆)·Ru₂(O₂CCF₃)₂(CO)₅] (4), in which the ligand is entrapped between two dimetal complexes. In contrast, when 3 is codeposited with [2. 2]paracyclophane, a new 1D polymeric product, [Ru₂(O₂CCF₃)₂(CO)₄·(₂-C₁₆H₁₆)] (5) has been isolated. Complexes 1–5 have been fully characterized by IR and NMR spectroscopy, as well as by X-ray diffraction.     

水溶性金属勒烯衍生物的合成和表征

金属富勒烯具有表面积大(2 nm2)、整体电中性、金属离子的解离常数Kd为0等独特的性质, 在医学上具有重要的应用价值[1～7]. 要将其用于生物体系, 需引入亲水基团. 水溶性Gd@C82(OH)x已被证实是一种比临床上应用的GdDTPA更好的核磁成像造影剂(其弛豫率比GdDTPA高20倍[7]), 并有望用作放射性示踪剂和放射性药物等, 且在生物体内外具有稳定性[2～6], 是生物医学上很有吸引力的材料. 本文在高效合成、分离纯化 Gd@C82的基础上合成了其多羟基衍生物、多取代氨基酸衍生物和多取代氨基磺酸衍生物, 并作了初步分析.