脂族酰基过氧化物分解动力学的研究(Ⅷ)——过氧化辛酰、过氧化己酰热分解产物的CIDNP效应

测定了过氧化辛酰(1)和过氧化己酰(2)在邻二氯苯中,分别在碘、碘乙烷、2-碘丙烷和3-溴丙烯存在下,90℃时热分解产物的¹HNMR谱,观察到自由基捕获产物(RX,R=n-C₇H₁₅、n-C₅H₁₁;X=I,Br)和歧化产物(R_-H)的CIDNP多重效应。讨论了过氧化酰热分解生成自由基对及相互作用的机理。     

Heterobimetallic Mo---Sn complexes. Reactions of [Mo(CO)3(CH3CN)2(Cl)(SnRCl2)] (R = Me, Ph) with 4(4-XC6H4)3 (X = Cl, F, H, Me, MeO)

Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO)₃(CH₃CN)₂(Cl)(SnRCl₂)] (R = Ph, Me) with P(4-XC₆H₄)₃ (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO)₂(CH₃COCH₃)₂(PPh₃)(Cl)(SnRCl₂)]·nCH₃COCH₃ (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO)₃{P(4-XC₆H₄)₃}(μ-Cl)(SnRCl₂)]₂ (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO)₃(CH₃CN) {P(4-XC₆H₄)₃}(Cl)(SnRCl₂)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes.     

The reactivity of cationic [trioxo-(1,4,7-triazacyclononane) rhenium(VII)] and oxorhenium(V) complexes containing triazamacrocycles

The reduction of colourless [LRe^VIIO₃]Br in an acetone-water mixture (6: 1) with zinc amalgam affords green, air-sensitive [LRe^VO₂Br] which forms a violet complex [LReO(μ-O)₂ReOBr₂]in aqueous solution (L = 1,4,7-triazacyclononane; C₆H₁₅N₃). From a similar reduction of [LReO₃]ReO₄ the violet neutral complex [LReO(μ-O)₂ReO(ReO₄)₂] was obtained. [LReO₃]⁺ is deprotonated in alkaline solution (pK_a = 10.3 + 0.2, 25°C) and [(C₆H₁₄N₃)ReO₃] was isolated as a yellow solid. The latter amido rhenium(VII) compound reacted in dimethylformamide with R---X (R = CH₃, benzyl; X = Cl), affording at the cyclic amine, N,N′,N″-trisalkylated complexes of the type [L′ReO₃]X. The monomeric rhenium(V) complexes [LReOX₂]X (X = Cl, Br, I) were obtained from the reaction of [n-Butyl₄N]ReOX₄ and L in acetonitrile. IR, UV-vis, ¹⁷O NMR spectra of these compounds are reported.     

相转移催化下4-氯苯磺酰基乙酸异丙酯的烷基化反应

在有机合成中可用芳磺酰基作暂时性活化基团。芳磺酰基乙酸酯是具有活性亚甲基的弱酸性化合物。通常要在氢化钠、醇钠存在下才能起烷基化反应。Ono等曾报道4-甲苯磺酰基乙酸甲酯在DBu存在下进行烷基化反应,但反应时间长。近年来,相转移催化在有机反应中的应用受到重视,然而用固液相转移催化法使芳磺酰基乙酸酯起烷基化反应还未见报道。我们在K₂CO₃/DMF体系中,用TEBA作催化剂,研究了4-氯苯磺酰基乙酸异丙酯与不同类型卤代烃所起的烷基化反应。合成了尚未见报道的一或二烷基化产物。     

非对称Schiff碱过渡金属配合物模拟酶催化烯烃环氧化(Ⅰ)

研究了温和条件下以亚碘酰苯为氧源,非对称性的和对称性的Mn(Ⅲ)Schiff碱配合物[Mn(Ⅲ)(CBP－phen－Xsal)Cl,X=H,Cl,Br,NO₂,CH₃,OCH₃]和[Mn(Ⅲ)(CBP－R－CBP)Y,R=CH₂CH₂－,－CH(CH₃)CH₂－,－C₆H₄－;Y=Cl,OCH₃]催化非官能性烯烃苯乙烯、环己烯和α-甲基苯乙烯的环氧化反应.结果表明,非对称配合物Mn(Ⅲ)(CBP－phen－Xsal)Cl是一个良好的催化非官能性烯烃环氧化反应的催化剂体系;中心金属离子Mn(Ⅲ)的电子结合能越小,催化环氧化效果越好;对上述3种烯烃环氧化物最好收率分别达到73％、100％和92％.     

Synthesis and decomposition of neutral palladium(IV) complexes containing fac-PdMe2R groups, including reductive elimination by η-propenylpalladium(IV) complexes to form η-propenylpalladium(II) species

Oxidative addition of ethyl iodide to PdMe₂(2,2′-bipyridyl) in (CD₃)₂CO gives the unstable “PdIMe₂Et(bpy)”, which undergoes reductive elimination to form PdIR(bpy) (R = Me, Et), ethane, and propane. Ethene and palladium metal are also formed, and are attributed to decomposition of PdIEt(bpy) via β-elimination. Similar results are obtained with n-propyl iodide, although a palladium(IV) intermediate was not detected, but CH₂=CHCH₂X (X = Br, I) and PhCH=CHCH₂Br give isolable complexes fac-PdXMe₂(CH₂CH=CHR)(L₂) (R = H, Ph; L₂ = bpy, phen). The propenyl complexes decompose at ambient temperature to form ethane, a trace of PdXMe(L₂), and mixtures of [Pd(η³-C₃H₅)(L₂)]X and [Pd(η³-C₃H₅)(L₂)]-[Pd(η³-C₃H₅)X₂]; for fac-PdBrMe₂(CH₂CH=CH₂)(bpy) the major palladium(II) product is [Pd(η³-C₃H₅)(bpy)]Br.     

CIDNP of Diecyl Peroxides Studies on the Kinetics of Decomposition of Diacyl Peiroxides Ⅷ in the Decomposition of Diacyl Peroxides

H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)2 R=n-C H (1),n-c5H11(2)) in ODCB in the presence of scavengers,such as I2C2H5I,(CH3)2CHI,and CH2=CHCH2 Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R-H.The reactionmechanism is discussed in terms of radical pair theory.     

Solution-state conformations of 2-fluoro-, 2-chloro- and 2-bromo-acetophenone: a dipole moment and kerr effect study

Experimental dipole moments and infinite-dilution Kerr constants for 2-fluoro-, 2-chloro and 2-bromo-acetophenone (CH₃COC₆H₄X; X = F, Cl, Br) as solutes in CCl₄ at 25°C are analysed, yielding the following effective dihedral angles and percentage abundances of the less stable XO-cis conformers: X = F, 10 ± 10°, 5 ± 5%; X = Cl, 40 ± 5°, 10 ± 5%; and X = Br, 65 ± 10°, 25 ± 10%.     

二元和三元复合物中阳离子硫键与磷键的理论研究

采用MP2/cc-pVDZ和cc-pVTZ基组分别对复合物XH₂S⁺…NCH₂P和NCH₂P…PyX(X=NH₂, CH₃, H, CN, F, Cl, Br)中的硫键和磷键进行了研究, 讨论了键长、 键临界点的电荷密度(ρ)、 拉普拉斯密度(▽²ρ)、 范德华表面穿透距离、 二阶稳定化能和电荷转移量对硫键和磷键相互作用能的影响. 结果表明, 当取代基X为吸电子基团时, 形成的硫键较强. 当X为给电子基团时, 形成的磷键较强. 利用能量分解方法分析了取代基—CN导致硫键稳定性反常的可能原因. 还进一步讨论了三元复合物H₃S⁺…NCH₂P…PyX(X=NH₂, CH₃, H, CN, F, Cl, Br)中硫键和磷键的协同相互作用以及取代基对复合物稳定性的影响. 并通过对比相同的2种单体在三元复合物和二元复合物中的二阶稳定化能和相互作用能的差值, 说明了硫键与磷键起到相互促进的正协同作用, 增强了三元复合物的稳定性.     

(Dimethylaminoethyl)cyclopentadienyl-liganden in der chemie von gruppe-13-elementen (Al, Ga, In

The synthesis of cyclopentadienyl complexes containing polydentate C₅R₄(CH₂CH₂NMe₂) ligands (R = H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C₅Me₄CH₂CH₂NMe₂) AlX₂ (X = Me, Cl, Br, I), (C₅Me₄CH₂CH₂NMe₂)MCl ₂ (M = Ga, In), (C₅H₄CH₂CH₂NMe₂)AlX₂ (X = H, Me, Et, Cl), (C₅H₄CH_2- CH₂NMe₂)GaCl₂,and (C₅H₄CH₂CH₂NMe₂)InMe₂ are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes.     

Formation of (η-R5C5)Ru(NO)X2 by the nitrosylation of (η-R5C5)Ru(CO)2X under irradiation

The ruthenium(II) complexes (η-R₅C₅)Ru(CO)₂X with R = H, CH₃ and X = Cl, Br, I undergo a facile reaction with nitric oxide under UV irradiation to afford ruthenium(IV) nitrosyl derivatives of the general type (η-R₅C₅)Ru(NO)X₂.     

Anchimeric assistance by γ-substituents Z, Z=MeO, PhO, MeS or PhS, in reactions of the bromides (Me3Si)2(ZMe2Si)CSiMe2Br with AgBF4

The new organosilicon bromides (Me₃Si)₂(ZMe₂Si)CSiMe₂Br with Z=PhO or MeS have been prepared and new spectroscopic data obtained for the previously reported compounds with Z=H, F, Br, Me, Ph, MeO or PhS. Competitions between pairs of bromides for a deficiency of AgBF₄ in Et₂O, with the determination of the ratio of the fluoride products by ¹⁹F-NMR spectroscopy, have led to the following approximate relative reactivities of the bromides and so to the relative abilities of the γ-Z groups to provide anchimeric assistance to the leaving of Br⁻ in this reaction: Me, 1; Ph, 40; PhO, 3400; PhS, 5000; MeS, 7000; MeO, 54 000. In methanolysis in CH₂Cl₂, (Me₃Si)₂(MeOMe₂Si)CSiMe₂Cl has been found to be roughly 120 times as reactive as (Me₃Si)₂(PhOMe₂Si)CSiMe₂Cl. Combination of the results with previously available information suggests the following approximate order of ability of γ-groups Z to provide anchimeric assistance in reactions at the Si---X bonds in compounds (Me₃Si)₂(ZMe₂Si)CSiMe₂X: OCOMe>OMe>OCOCF₃>MeS>PhS, PhO>N₃, Cl>NCS>Ph>CH=CH₂>Me.     

Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L=AN, CO, P(OMe)3; AN=acetonitrile) and CpFe(CO)L′X (L′=CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I)

Treatment of ruthenium complexes [CpRu(AN)₃][PF₆] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)₂X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Cl, Br, I) in refluxing CH₂Cl₂ for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)₂X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)₂][PF₆] (1b: L=CO, 1c: P(OMe)₃) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]₂ was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH₂Cl₂ at room temperature to give 3a, and transforms into 7a by the reaction with PMe₃.     

Reactivity of niobocene dihalogenides toward nitroso derivatives. EPR and IR characterization of the first niobium(IV) complexes containing an ArNO-N,O ligand

The reaction of [Nb(η⁵-C₅H₄R)₂X₂] [1: R = SiMe₃, X = Cl; 2: R = SiMe₃, X = Br; 3: R = H, X = Cl; 4: R =^t, X = Cl] with nitroso derivatives ArNO [a: Ar = Ph; b: Ar = o-CH₃-C₃H₄; c: Ar = p-(CH₃)₂NC₆H₄] yields paramagnetic complexes formulated as [Nb(η⁵-C₅H₄R)(η³-C₅H₄R)X₂(ArNO-N,O) 1a, 1b, 1c, 2a, 3a, 4a and 4c, which have been characterized by ESR and IR spectroscopy.     

Conformational energies, rotational barrier heights and molecular structures in C(CH2X)4 molecules (X=F, Cl, Br)

The conformational energies, rotational barrier heights and molecular structures in C(CH₂X)₄ molecules (X=F, Cl, Br) based on molecular-mechanics calculations have been obtained. The results from these calculations are compared with the experimental gas-phase results.     

Cyclic aryleneazachalcogenenes. Part III [1] synthesis of polyfluorinated 2,1,3-benzothia-(selena) diazoles

1-(4-X-Tetrafluorophenyl)-3-trimethylsilyl-1,3-diaza-2- thiaallenes (X = H, CH₃, Br, F, CF₃) treated with CsF in acetonitrile or THF cyclized to 6-X-4,5,7-trifluoro-2,1,3-benzothiadiazoles whose reduction led to the corresponding 1,2-diamino- benzenes. Cyclization of the latter with SeCl₄ gave 6-X-4,5,7- trifluoro-2,1,3-benzoselenadiazoles.     

两步沉积法制备Br或Cl掺杂的有机-无机杂化钙钛矿太阳电池

采用控制前驱体浓度的两步沉积法和插入PbI₂层的DMSO分子（PbI₂（DMSO）复合体）分别与MAX（MA=CH₃NH₃,X=I,Br）或MAX（X=I,Cl）进行的分子内交换法,实现了Br或Cl的掺杂并合成了厚度为300nm左右的混合卤化物钙钛矿MAPbI_3-xBr_x和MAPbI_3-xCl_x膜。MAX前驱体溶液中含5%（摩尔分数,下同）MABr或15% MACl所生成的Br或Cl掺杂钙钛矿膜能提高钙钛矿太阳电池的光伏性能,进一步提高MABr或MACl的含量并不会明显改变掺杂量,但会形成小的白色颗粒或者针孔,这些将对电池的性能产生不利影响。前驱体溶液含5% MABr的MAPbI_3-xBr_x钙钛矿太阳电池所获得的能量转换效率（PCE）为13.2%,含15% MACl的MAPbI_3-xCl_x钙钛矿太阳电池获得了最高13.5%的PCE。     

Photochemistry of perfluoroacyl halides in the presence of O2 and CO

Photolyses of CF₃C(O)X and C₂F₅C(O)X (X=Cl, F) at 254 nm in the presence of O₂ yield the perfluorinated radicals C₂F₅O (C₂) and CF₃O (C₁), respectively. The C₂ radicals decompose to give CF₃ radicals:

C₂F₅O→CF₃+CF₂O

which, in turn, react with O₂ leading to the formation of C₁ radicals. When in addition to O₂, CO is present, the C₁ radicals react with it leading to its catalytic oxidation to CO₂. The trioxide CF₃OC(O)O₃C(O)OCF₃ was observed following the photolysis of all four halides in the presence of O₂ and CO.

The other radical partners coming from the initial step in the photolysis (XC(O)) as well as the products of their reaction with O₂ (XC(O)O_y, y=1, 2) do not react with CO but when X=F they lead to the formation of a new stable peroxy molecule with the formula CF₃OC(O)O₂C(O)F. Some of the properties of this new molecule, its stability and its IR features are presented in this work.     

硝酸异丙酯与Cl原子、 OH和NO3自由基反应的机理及动力学

采用CCSD(T)//M06-2X/6-311++G(d,p)方法, 结合传统过渡态理论, 研究了硝酸异丙酯与Cl原子、 OH及NO₃自由基的反应机理和动力学. 两个反应物单体首先形成氢键复合物, 随后X(X=Cl原子、 OH和NO₃自由基)提取硝酸异丙酯中叔碳的α-H原子或甲基的β-H原子, 室温下, 以X提取α-H原子为主. 反应的主要历程为 Cl原子(OH或NO₃自由基)提取(CH₃)₂CHONO₂的α-H原子, 生成HCl(H₂O或HNO₃)分子和(CH₃)₂CONO₂自由基, 后者分解为丙酮和NO₂. 结果表明, 在200~500 K温度范围内, 随着温度的升高, 丙酮和NO₂的产率降低; 在室温下, 硝酸异丙酯与Cl原子、 OH和NO₃自由基反应的速率常数分别为3.933×10^-11, 1.182×10^-13和7.134×10^-19 cm³·molecule^-1·s^-1. 计算所得硝酸异丙酯与OH自由基反应的动力学数据与实验结论一致.     

Synthesis and structural behavior of the P-functional organotin chlorides [Ph2P(CH2)3]2SnCl2, Ph2P(CH2)3SnCl2Me, and Ph2P(CH2)nSnCl3 (n=2, 3)

The P-functional organotin dichloride [Ph₂P(CH₂)₃]₂SnCl₂ (3) is synthesized by reaction of Ph₂P(CH₂)₃MgCl with SnCl₄ independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph₂P(CH₂)_nSnCl₂R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph₂P(CH₂)_nSnCy₃ (n=2, 3) with SnCl₄ or MeSnCl₃, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph₃PO)₂ (7) and 5(Ph₃PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data.