C60Pd(Ph2PCH2PPh2)配合物的合成及光电性能研究

Fulerene complexe C60 Pd（ Ph2PCH2PPh2）was perpared by the method of ligand substitution via the reaction of C60 with Pd（Ph2PCH2PPh2）2 under condition of a nitrogen atmosphere and refluxing,and the title compound was appraised and characterized by methods of elemental analysis,FT-IR,UV-vis,XPS and XRD. The results showed that the structure of purposeful product was that the Ph2PCH2PPh2 took up two coordination sites of the central metal,and C60 took up another two sites in σ-π feeback pattern. The porperties on photoelectricity,redox and thermostability of the title complexe were studied. The results of studying on photoelectricity showed that the photovoltaic effect of（n+n）heterojunction electrode formed by C60Pd（Ph2PCH2PPh2）/ GaAs was supper,especially in the BQ/ H2Q redox couple,and the greatest value of photovoltaic potential was up to 174 mV. The photovoltaic performance of C60Pd（Ph2PCH2PPh2）/GaAs electrode at 1 μm for thickness of C60Pd（Ph2PCH2PPh2）film was the best.     

(η2-C60)[Pd(pph3)2]n配合物的合成和光电性能研究

从1985年Kroto等[1]发现C60等富勒烯(球烯)至1996年富勒烯的发现者获诺贝尔化学奖期间,在化学、物理、材料等学科领域逐渐地形成了富勒烯的研究热潮[1,2].现在人们正以较多注意力投向富勒烯的各类衍生物结构与性能之间关系的研究,以期望在开发应用方面迈出更大的步伐.它首次合成出-系列的(η2-C60)[Pd(pph3)2]n(n=1、2、3、4)配合物,并比较这些在结构与组成上有差异配合物的光电转换性能.     

富勒烯系列配合物η2-C60[Ru(NO)(PPh3)]n的合成与光电性能

合成了一系列新的富勒烯钌配合物.通过元素分析、紫外-可见光谱、红外光谱、光电子能谱(XPS)和13C及31PNMR等多种手段对它们进行了表征.结果表明.该系列配合物分子内存在超共轭效应,共轭电子多.离域性好.通过光伏效应装置研究了它们的光电性能,结果显示该系列配合物具有良好的光电性能.     

C60Co(Pph3)2的合成和表征

The fullerene complexe C₆₀Co(Pph₃)₂ has been prepared by the reaction of C₆₀ with CoCl₂(Pph₃)₂ under a nitrogen atmosphere and refluxing， and characterized by elemental analyses， FT-IR， XPS， NMR， which appove that C₆₀ coordinates to Co(Pph₃)₂ group in σ-π pattern and the electron is super conjugate over whole molecule. The result of redox property study show that the reduction potentiel of C₆₀Co(Pph₃)₂ is more negative than that of C₆₀， the reason may be the π electron dentensity of C₆₀ in C₆₀Co(Pph₃)₂ increases， which lead to it′s electron affinity decreasing. The thermostability experiment indicates that the oxidation decomposition temperature of C₆₀Co(Pph₃)₂ is lower than that of pure C₆₀.     

C60RuH2(CO)(PPh3)配合物的合成和氧化还原性能研究

自从1985年Kroto等人发现C60等碳原子簇以来,在化学、物理以及材料科学掀起了富勒烯的研究热潮。目前富勒烯配合物的制备及其性质的研究是富勒烯化学最为活跃的研究领域之一,人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系,以期合成出具有特殊性能的富勒烯配合物,为富勒烯的实际开发应用奠定基础。本文合成表征了C60RuH2(OH)(PPh3)配合物,研究了其氧化还原特性。     

C60Pt(BINAP)金属配合物的合成表征与光电性能研究

本文利用配体取代法合成了C60Pt(BINAP)新型富勒烯膦金属配合物,采用质谱、元素分析、紫外.可见吸收光谱、红外吸收光谱、光电子能谱等对该产物进行了表征,并测定了其在光化学电池中的光伏效应.光伏效应测试结果表明:在BQ/H2Q与I2/I3-介质溶液中镀层厚度为1～2μm时,具有较好的光电转换性能,光生电压值最高达358 mV.     

（η^2—C70）Pd（PPh3）2）配合物的合成和光电性能研究

在惰性气氛中由取代反应合成出（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２配合物，在光电化学电池中测定了（η２－Ｃ７０）Ｐｄ（ＰＰｈ３）２在ＧａＡｓ电极上形成的ｎ＋ｎ型异质结光伏效应，结果表明，在Ｉ２／Ｉ３电对介质中（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２有较大的光伏效应值；当（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２的薄膜厚度为１μｍ时光伏效应最大；（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２在ＧａＡｓ电极上的光电转换性能     

金属配合物[MBr{(Ph2PCH2CH2)2C6H3}],[M=Pd(Ⅱ)、Pt(Ⅱ)]的合成及晶体结构

合成了一个新的双膦配位体2,6-双(二苯基膦乙基)溴苯,通过Pd     

双(二苯基膦戊烷)富勒烯合铂配合物的合成及光电性能

采用配体取代法合成了以双二苯基膦戊烷（dpppe）及C60为配体、Pt为中心金属的C60Pt(dpppe)新型富勒烯膦金属配合物。 运用质谱、元素分析、紫外-可见吸收光谱、红外吸收光谱和光电子能谱等测试技术对产物进行了表征,同时采用循环伏安法对目标产物进行氧化还原性能研究。 结果表明,C60与金属Pt配位后还原电位发生负移。 结合电子光谱数据确定了目标产物的能级结构,其最高占有轨道和最低非占轨道能级分别为5.635和3.815 eV。 还考察了目标产物在光化学电池中的光伏效应,测试结果表明,在 BQ/H2Q介质溶液中镀层厚度为 1~2 μm 时,具有较好的光电转换性能,光生电压值最高达358 mV。     

富勒烯的金属配合物及其催化性能

富勒烯的金属配合物及其催化性能１）刘英陈远荫２）盛蓉生（武汉大学化学系武汉４３００７２）关键词富勒烯金属配合物催化分类号Ｏ６４３．３２碳元素的第三种存在形式富勒烯正以其独特的结构和性能以及诱人的应用前景引起人们日益浓厚的兴趣．其中又以Ｃ６０的研究为主...     

C60Pd（Ph2POCH2CH2OPPh2）的合成与光电转化性能

C60Pd（Ph2POCH2CH2OPPh2）的合成与光电转化性能;富勒烯;钯配合物;光电性能     

Synthesis and electrochemical behaviour of the cyanamide-isocyanide complexes of rhenium, trans-[ReL(CNR)(Ph2PCH2CH2PPh2)2] ( L = NCNH2 or NCNH)

Reaction of trans-[ReCl(CNR)(dppe)₂] (R = Me (Ia) or ^tBu (Ib); DPPE = Ph₂PCH₂CH₂PPh₂) in CH₂Cl₂ with cynamide in the presence of TlBF₄ forms the new cynamide-isocyanide complexes trans-[Re(CNR)(NCNH₂)(dppe)₂][BF₄] (R = Me (IIa) or ^tBu (IIb)), which upon treatment by ^tBuOK or Et₃N give trans-[Re(NCNH)(CNR)(dppe)₂] (R = Me (IIIa) or ^tBu (IIIb)). The electrochemical behaviour of these species was studied by cyclic voltammetry and controlled potential electrolysis at a Pt electrode in an aprotic solvent, and cathodic reduction of II results in the formation of III.     

The hydrogenolysis of C60 and C70

Temperature-programmed reaction (TPR) of C₆₀ and C₇₀ with H₂ was carried out on nickel in order to investigate the thermal stability of the fullerenes in the catalytic hydrogenation. The TPR profiles showed two methanation peaks and the corresponding weight decrease above 420°C, indicating the hydrogenolysis to CH₄. This revised version was published online in June 2006 with corrections to the Cover Date.     

Reactions of allylic compounds such as allyl alcohols,allyl ethers,and allylamines using trans-Mo(N2)2(Ph2PCH2CH2PPh2)2

Double-bond migration of allylic alcohols and allylic alkyl ethers was catalytically effected with trans-Mo(N₂)₂(dpe)₂(dpe = Ph₂PCH₂CH₂PPh₂). Decarbonylation occurred simultaneously in the case of allyl alcohol. Diallyl ether and allyl phenol ether gave the fragmentation products presumably through initial oxidative addition of the allylO bond. Allylamine was converted to N-propylideneallylamine and NH₃. N,N-Dimethylallylamine was isomerized to N-trans-propenyldimethylamine, which was further transformed into 4-dimethylamino-1,3-hexadiene and dimethylamine on addition of oxygen. The catalytic allylation of methyl acetoacetate with allylic ethers and amines was achieved by use of trans-Mo(N₂)₂(dpe)₂.     

The CO and CS bond cleavage in carbon dioxide and tolyl isothiocyanate by reactions with the Mo(0) tetraphosphine complex [Mo{meso-o-C6H4(PPhCH2CH2PPh2)2}(Ph2PCH2CH2PPh2)]

A Mo(0) complex containing a new tetraphosphine ligand [Mo(P₄)(dppe)] (1; P₄ = meso-o-C₆H₄(PPhCH₂CH₂PPh₂)₂, dppe = Ph₂PCH₂CH₂PPh₂) reacted with CO₂ (1 atm) at 60 °C in benzene to give a Mo(0) carbonyl complex fac-[Mo(CO)(η³-P₄O)(dppe)] (2), where the O abstraction from CO₂ by one terminal P atom in P₄ takes place to give the dangling P(O)Ph₂ moiety together with the coordinated CO. On the other hand, reaction of 1 with TolNCS (Tol = m-MeC₆H₄) in benzene at 60 °C resulted in the incorporation of three TolNCS molecules to the Mo center, forming a Mo(0) isocyanide-isothiocyanate complex trans,mer-[Mo(TolNC)₂(η²-TolNCS)(η³-P₄S)] (4), where the S abstraction occurs from two TolNCS molecules by P₄ and dppe to give the η³-P₄S ligand and free dppeS, respectively, together with two coordinated TolNC molecules. The remaining site of the Mo center is occupied by the third TolNCS ligating at the CS bond in an η²-manner. The X-ray analysis has been undertaken to determine the detailed structures for 2 and 4.