四核钴羰基簇合物的合成和晶体结构

用Co₂(CO)₈与有机杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)NC(Me)(R=Me,Et)反应,得到两类4个含S,P桥基配体的四核钴羰基簇合物Co₄(CO)₁₀(μ₄-S)[μ₄-P(C₆H₄OR)](1:R=Me;3:R=Et)和Co₄(CO)₁₀(μ₃-S)[μ₂-P(C₆H₄OR)N(C₆H₅)NC(Me)](2:R=Me,4:R=Et).在反应中,前配体中的PS键以及C-S,P-S,P-N键劈开,产生的分子片与金属钴原子配位,组建成新的羰基钴簇.对这4个簇合物进行了元素分析,IR,¹HNMR和MS谱学表征,并测定了簇合物4的晶体结构,该晶体属单斜晶系,P2₁/c空间群,晶胞参数a=1.9065(4)nm,b=1.0081(2)nm,c=1.6663(3)nm,β=97.36(3)°,V=3.1704(11)nm₃,Z=4,D_c=1.743g/cm³.Co1Co3Co4呈三角形分布,其中Co-Co平均键长为0.251nm,而Co₂在该三角平面的一侧,Co2-Co3键为0.269nm.该簇合物分子骨架为三角钉型结构,每个Co原子的立体几何均为变形八面体,但配位环境各不相同.     

Synthesis and Characterizations of New Ferrocenyl Schiff Base with NLO Responses

IntroductionThereisconsiderableinterestinmaterialswithNLO(nonlinearoptics)propertiesinthepasttenyears"2.lthasstatedthattheuseoforganometalliccompoundswithNLOhasawidefanofadvantages'thatmakethemappropriateinthefieldofnonlinearoptics.ItispossibletobeusedaspromisingmateriaIbecauseofstabilityofferrocenylcomplexestoheatandoptics.Recently,K.R.J.Thomaset.al4haveinvestigatednewferrocenebaseddonor-acceptorcomplexescontainingthiopheneandfuranintheconjugationchain.Inthesecase,theimportanceofthepush-…     

Chalcogen-Containing Manganese Carbonyl Clusters: Synthesis and Structural Transformations

Recently, we have developed several synthetic routes to the new classes of chalcogen-containing manganese carbonyl clusters, and the interesting structural transformations and reactivity of the resultant clusters have been investigated as well. In this short review, the syntheses and bonding modes of the sulfur, selenium, and tellurium-containing manganese carbonyl complexes reported by our laboratory will be presented, and the cluster growth and transformation will be systematically compared and discussed.     

Pt羰基簇合物在NaY内的合成机理

利用IR，EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n＝3,4)在NaY分子筛超笼内的合成机理．在氧化样品Pt~(2+)/NaY上300－373 K的还愿羰基化过程中，首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)＝2110 cm~(-1))，然后聚集成“Pt_3(CO)_6”(σ_(CO)＝2112，1896和1841 cm~(-1))，最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)＝2080，1824 cm~(-1))．“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换，而[Pt_3(CO)_6]~(2-)_n(n＝3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢，室温下，NO能逐步破坏Pt羰基簇合物的层间和层内Pt－Pt键，得到中间物种“Pt_3(CO)_6”和PtO(CO)，同时在气相产生CO_2和N_2O．而由上述两中间物种出发，300－353 K温度下，在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物．     

RP-Bridged Metal Carbonyl Clusters: Synthesis,Properties, and Reactions

Metal carbonyl clusters possess a complicated chemistry that is only beginning to be understood. One of the main current goals in this area is thus an understanding of their reactivity. This article describes the syntheses and reactions of clusters that contain metal carbonyl fragments bridged by a main-group element. But what is the sense of making such clusters still more complicated by the incorporation of main-group elements? The example of μ₃-bridged carbonyl clusters will serve to show that the main-group element plays an important role in the study of reaction paths; it holds the metal carbonyl fragments together even when the bonds between them are broken in the course of a reaction. Trinuclear μ₃-bridged clusters prove to be small enough to allow the analysis of typical cluster reactions (such as the reversible breaking of metal-metal bonds) in terms of single reaction steps. They are also large enough to provide surprises by their multifaceted reactivity. It will be shown that a detailed study of trinuclear RX-bridged metal carbonyl clusters (X ? N, P, As, Sb, Bi)—a very small part of carbonyl cluster chemistry—can lead to a better understanding of the general reaction principles involved.     

含偶磷氮烷配体的三核钌羰基簇合物的合成和晶体结构

用Ru₃(CO)₁₂与顺-2,4二(叔丁基胺基)-1,3,-二(叔丁基)-1,3,2,4-环偶磷氮烷cis-[P(NHBu^t)NBu^t]₂反应,得到两个新的含偶磷氮环的三核钌羰基簇合物:Ru₃(CO)₁₁[{P(NHBu^t)NBu^t}₂] Ⅰ和Ru₃(CO)₁₁[P(NHBu^t)(NBu^t)₂P(O)H] Ⅱ。对它们进行了元素分析,IR和¹H NMR谱表征,并用X-ray单晶衍射法测定了晶体结构。Ⅰ:正交晶系,Pna2(1)空间群,a=2.7574(9) nm,b=0.8981(3) nm,c=1.5272(5) nm, V=3.782(2) nm³,D_c=1.686 g·cm^-3,Z=4;Ⅱ:三斜晶系,P1空间群,a=0.96384(19) nm,b=1.1705(2) nm,c=1.5589(3) nm,α=101.72(3) °,β=91.54(3) °,γ=108.20(3) °,V=1.6282(6)nm³,D_c=1.845g·cm^-3,Z=2;两个簇合物均为Ru₃(CO)₁₂的单取代衍生物,配位基环偶磷氮烷以单齿P原子配位在一个Ru原子的赤道位置上。Ⅱ中,偶磷氮环上未配位P(Ⅲ)被氧化成具有膦酰基结构(=P(O)H)的P(Ⅴ)。     

High-Yield Synthesis of New Ni–Ru Carbido–Carbonyl Clusters

Four new bimetallic Ni–Ru mixed-metal carbido–carbonyl clusters of a general formula [NiRu₅C(CO)₁₄ L₂], where L₂ = dppe (2), dppp (5), (PPh₃)₂ (8) and (PBu₃)₂ (13) were synthesised following the general synthetic strategy using penta- and hexaruthenium carbido carbonyl dianions in the reactions with corresponding dichloro complexes of Ni(II). The molecular and crystal structures of 2, 5, 7, 8, and 13 were determined by single crystal X-ray analysis. The mixed-metal core is octahedral with the P atoms coordinating to the Ru atoms.     

Synthesis and Characterization of Bimetallic Nickel and Cobalt Carbonyl Complexes Containing Stannyl Groups

The bimetallic NiSn₂ complex Ni(SnBu₃^t)₂(CO)_3, 1, was obtained from the reaction of Ni(COD)₂ and Bu₃^tSnH and CO. The reaction of Co₂(CO)₈ and Bu₃^tSnH afforded the bimetallic Co–Sn complex Co(SnBu₃^t)(CO)₄, 3. Compound 3 was also obtained from the reaction of Co₄(CO)₁₂ and Bu₃^tSnH but in a lower yield. Both compounds 1 and 3 were characterized by single crystal X-ray diffraction, and possess trigonal bipyramidal geometries around the transition metal centre with two and one stannyl ligands, respectively.     

Synthesis of Polymer-Supported Heteronuclear Rhodium- Cobalt Bimetallic Carbonyl Cluster Catalysts and Their Hydroformylation Properties

Tetranuclear Rh-Co bimetallic cluster was synthesized and characterized by IR and XPS. The properties of the anchored catalysts, its stability and the ligand effect were also studied. The experimental results show that the optimal conditions for the hydroformylation of hexene-1 are as follows: the temperature is 80℃, reaction time 8 h, pressure 5. 88×105 Pa, and molar ratio of H2/CO 1. 2/1. 0. Functional groups attached to the donor atom(N) possess more or less some influence on the catalytic behavior. Compared with the homogeneous cluster, the polymer-supported bimetallic cluster is more stable. After the catalytic reaction, the structure of the anchored catalysts was not destroyed. X-ray photoelectron spectroscopy characterization indicates that there is a weak interaction between the polymer support and the active metals.     

Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry

Two new tetraosmium carbonyl clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (1) and [Os₄(-H)₄(CO)₁₀{ ²-NC₅H₄(N=N)C₆H₅}] (2) were synthesized from the reaction of [Os₄(-H)₄(CO)₁₂] with two equivalent of 2-phenylazopyridine ligand in dichloromethane at ambient temperature using trimethylamine-N-oxide as the decarbonylation reagent. Subsequent chromatographic purification led to the isolation of 1and 2as stable orange and blue solids in respectively 25 and 13% yields. Complex 1converted to 2in a 25% yield in refluxing chloroform. Treating a solution of [Os₄(-H)₄(CO)₁₂] in dichloromethane with two equivalent of 3-phenylazopyridine led to the formation of another two new clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (3) and [Os₄(-H)₄(CO)₁₀(NMe₃){ ¹-NC₅H₄(N=N)C₆H₅}] (4), which could be isolated as yellow solids in 34% and 21% yields respectively. Thermolysis of 3or 4in refluxing n-hexane gives [Os₄(-H)₃(CO)₁₀{- ³-NC₅H₃(N=N)C₆H₅}] (5) in 24 and 33% yields respectively. Their electronic absorption properties and electrochemical behavior are also reported.     

铑钴四核簇合物的合成表征及其对苯乙烯的氢甲酰化反应性能的研究

研究表明，含有铑原子的异多核过渡金属羰基簇合物在一些催化反应中具有好的催化活性；有机膦是比羰基配位能力更强的一类配体，与簇合物中的金属配位后可使簇合物更趋稳定．过渡金属羰基簇合物骨架在催化反应过程中是否能够保持完整性一直是簇合物催化研究领域中的问题之一．为此，我们合成了标题簇合物2(n=1)和3(n=2)，     

二茂铁氨基化合物的合成

二茂铁与邻甲氧基苯甲酰氯反应生成邻甲氧基苯甲酰基二茂铁,再与一系列芳胺反应合成亚胺,最终还原为二茂铁氨基化合物,其结构均经元素分析、^1H NMR确证。     

分子筛笼内金属羰基簇合物的热稳定性研究

本实验采用戊马比妥钠诱发豚鼠和家兔急性心力衰竭模型，观察了舒心丸的治疗作用。结果表明，舒心丸ｉｖ能明显升高心衰豚鼠的心脏收缩幅度和心衰家兔的Ｂｐ，ＬＶＰ，ＬＶ±ｄｐ／ｄｔ和ＣＯ。其作用与哇巴因相似。     

含硫磷桥基的两核铁羰基簇合物的合成和晶体结构

Fe3(CO)12与杂环二硫代次膦酸盐SP(C6H4OR)(S)N(C6H5)NC(Me)(R=Me,Et)反应,得到两个新的含硫磷桥基的双核铁羰基簇合物Fe2(CO)6[μ-η2-SC(Me)NN(C6H5)P(C6H4OMe)](Ⅰ)和Fe2(CO)6[μ-η2-SC(Me)NN(C6H5)P(C6H4OEt)](Ⅱ),以及簇合物Fe3(CO)9(μ3-S)2(已知).对它们进行了元素分析,IR,1HNMR和MS等谱学表征,并用X-ray衍射技术测定了(Ⅰ)的晶体结构.该晶体属单斜晶系,P2(1)/n空间群,晶胞参数a=11.192(2)A,b=14.272(3)A,c=16.281(3)A,β=108.22(3).,V=2470.2(8)A3,Z=4.两核簇合物中含有两个桥基Fe-S-Fe和Fe-P-Fe,而且-C(7)-N(2)-N(1)-链连结在S、P原子间,形成了两个六员螯环Fe(1)SCNNP和Fe(2)PNNCS,增强了簇合物的稳定性.     

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.     

具有含磷、硫配体的二核和三核钌羰基簇合衍生物的合成及晶体结构

用Ru₃(CO)12与杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)NC(Me)(R=Me,Et)反应,得到两类4个含磷、硫配体的二核和三核钌羰基簇合衍生物Ru₃(CO)₈(μ₃-S)₂[P(C₆H₄OR)N(C₆H₅)NC(Me)S](1;R=Me;3;R=Et)和Ru₂(CO)₆[μ-η₂-SC(Me)NN(C₆H₅)P(C₆H₄OR)](2;R=Me;4;R=Et).对它们进行了元素分析、IR、¹HNMR和MS谱学表征,并用X射线衍射技术测定了1和2的晶体结构.晶体1属三斜晶系,P1空间群,晶胞参数a=1.0755(2)nm,b=1.5760(2)nm,c=0.9078(1)nm,α=98.12(7)°,β=96.64(4)°,γ=79.67(5)°,V=1.4921(4)nm³,Z=2,R(wR)=0.0303(0.0615);该簇合物分子为开口三核钌簇,其簇骨架Ru₃(μ₃-S)₂为畸变四方锥构型;五元杂环上的P原子取代在Ru1原子的轴向配位位置上.晶体2属单斜晶系,P2(1)/n空间群,晶胞参数a=1.1243(4)nm,b=1.4105(5)nm,c=1.62945(7)nm,β=107.06(5)°,V=2.4702(2)nm³,Z=4,R(wR)=0.0248(0.0441);两核簇合物分子中含有2个六元螯环Ru1SCNNP和Ru2SCNNP,增强了簇合物的稳定性.     

Recent Developments of Tellurium- and Selenium-Containing Iron Carbonyl Clusters

In recent years, quite a number of tellurium-or selenium-containing iron carbonyl clusters have been synthesized and structurally characterized, and some interesting structural transformations and reactivity of these clusters have been systematically investigated as well. The syntheses and reactivity of these clusters are reviewed and compared.