硅基取代及硅桥连双环戊二烯基四羰基二铁与HgCl2的反应及产物结构研究

二(硅基取代环戊二烯基)四羰基二铁化合物[η~5-RC_5H_4Fe(CO)]_2(μ-CO)_2(R=SiMe_3,1;Si_2Me_5,2)与HgCl_2反应得到预期的Fe—Fe键被断裂的铁氯化物6(R=SiMe_3)和8(R=Si_2Me_5)及铁氯汞化物5(R=SiMe_3)和7(R=Si_2Me_5).硅桥连的类似物R~1[η~5-C_5H_4Fe(CO)]_2(μ-CO)_2(R~1=SiMe_2,3;SiMe_2OSiMe_2,4)由上述反应除得到预期产物外,还分离到相应的歧化产物R~1[η~5-C_5H_4Fe(CO)_2HgCl]_2(R~1=SiMe_2,10;SiMe_2OSiMe_2,13)与R~1[η~5-C_5H_4Fe(CO)_2Cl]_2(R~1=SiMe_2,11;SiMe_2OSiMe_2,14),讨论了歧化产物的生成原因.对产物5～14的结构用元素分析、IR,~1H NMR进行了表征,并测定了5的晶体结构.5为单斜晶系,空间群P2_1/n,α=1.1648(3),b=0.7484(4),c=1.6823(5)nm,β=106.55(2)°,V=1.405(2)nm~3,Z=4,D_x=2.29g·cm~(-3).     

Photophysical Performance and Energy Transfer Mechanism of a 1-D Chain-like Complex

By means of solvothermal reactions, a novel lanthanide-mercury compound, {[Ho(IA)_3(H_3O)_2]_(2n)[2n(HgCl_4)][n(HgCl_5)]}·3nH_3O·nH_2O(1, HIA = isonicotinc acid) was prepared and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2147(5), b = 20.8106(4), c = 15.3060(3) ?, β = 128.326(2)°, V = 6050.8(2) ?~3, C_(36)H_(45)Cl_(13)Hg_3Ho_2N_6O_(20), Mr = 2274.26, Z = 4, D_c = 2.497 g/cm~3, μ(Mo Kα) = 10.817 mm~(-1) and F(000) = 4232. It exhibits a one-dimensional(1-D) chain-like structure. Solid-state photoluminescence measurement shows that it displays brown light emission bands. These emission bands originate from the characteristic emissions of the 4 f electrons intrashell transitions of ~5S_2 → ~5I_8 and ~5F_5 → ~5I_8 of the holmium(Ⅲ) ions in 1. The photoluminescence emission energy transfer mechanism is elucidated by the energy level diagrams of the holmium(Ⅲ) ions and isonicotinic acid ligand. Complex 1 has CIE chromaticity coordinates of(0.4361, 0.4992). Solid-state UV/Vis diffuse reflectance spectra reveal that it possesses wide optical band gap of 4.94 eV.     

(1,1,2,2-四甲基二硅桥连)双(四甲基环成二烯基)四羰基二铁与碘的反应

标题化合物(Me_2SiSiMe_2)[η~5-(C_5Mc_4)Fe(CO)]_2(μ-(CO)_2(1)与碘在苯中反应,生成碘插入Fe—Fe键的碘正离子桥连二铁化合物(Me_2SiSiMe_2)[η~5-(C_5Me_4)Fe(CO_2)]_2I_n~+.I_n~-(n=3,3;n=5,4).如反应在氯仿中进行,则只能分离到Fe—Fe键断裂的双铁碘化物(Me_2SiSiMe_2)[η~5-(C_5Me_4)Fe(CO)_2I]_2.将4溶于Me_2SO/Me_2CO中,则其分子内的I_5~-与Fe—I~+—Fe两部分相互作用,也生成碘桥断裂的产物.以元素分析、IR、~1H NMR谱表征了2～4的分子结构,并经X射线衍射测定了2的晶体及分子结构.     

Upconversion Photoluminescence and Energy Transfer Mechanism of a Novel Terbium-mercury Compound

A novel terbium-mercury complex [Tb(IA)_3(H_3 O)_2]_2 n(2 n HgCl_4)(n Hg_2 Cl_5)·n H_3 O· 3 n H_2 O(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2347(5), b = 20.8342(6), c = 15.3206(3) ?, β = 128.257(2)°, V = 6074.3(2) ?3, C_(36)H_(41)Cl_(13)Hg_4N_6O_(20)Tb_2, Mr = 2458.80, Z = 4, D_c = 2.689 g/cm~3, μ(Mo Kα) = 13.014 mm~(–1) and F(000) = 4520. The crystal structure of 1 is characterized by a one-dimensional(1-D) chain-like structure. Solid-state UV/Vis diffuse reflectance spectrum reveals the existence of a wide optical band gap of 3.36 eV. Solid-state photoluminescence experiment uncovers that it shows reddish brown upconversion emission. The emission bands are originated from the characteristic emission of the 4 f electrons intrashell transition of the ~5D_4 → ~7 F_J(J = 6, 5, 4) of the Tb~(3+) ions. Energy transfer mechanism is explained by the energy level diagram of the Tb~(3+) ion and the isonicotinic acid ligand. It shows a remarkable CIE chromaticity coordinates(0.4158, 0.4005).     

VO(NCS)_n~((2-n) )配合物的ESR波谱及其稳定常数的测定

本文研究了VO(NCS)_n~(2-n)~ 配合物的ESR波谱,指出VO~(2 )与SCN~-在乙二醇-水混合溶剂中可形成四种不同组成的配合物:VONCS~ ,VO(NCS)_2,VO(NCS)_3~-,VO(NCS)_4~(2-).测定了ESR波谱参数,该配合物的超精细耦合常数A与SCN~-配位数n呈线性关系,A_n=117.66—3.41n(G).根据 ESR 波谱计算了配合物VO(NCS)_n~(2-n)~ (n=1,2,3,4)的逐级稳定常数,log K_1=2.15,log K_2=1.55,logK_3=0.8 7,log K_4=0.22.其中K_3,K_4的测定在文献上尚未见过报道。     

Synthesis,Structure and Properties of a New Terbium(Ⅲ) Complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2

A new terbium(Ⅲ) complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2 has been synthesized with 2-(4-methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/n,a=15.0786(6),b=13.5762(5),c=22.9683(9) A,β=104.130(4)°,V=4559.6(3) A~3,D_c=1.540_g/cm~3,Z=2,μ(MoKα)=1.615 mm~(-1),F(000)=2136,the final R=0.0528 and wR=0.0740.The Tb(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+5)D_4→~7F_6(490 nm),~5D_4→~7F_5(546 nm),~5D_4→~7F_4(588 nm) and ~5D_4→~7F_3(622 nm).The complex is an antiferromagnet in the range of 300～2 K.Also reported in the paper is the thermal stability property of the title complex.     

B_n(BO)_n~(2-)、CB_(n-1)(BO)_n~-和C_2B_(n-2)(BO)_n(n=5~12):类似于笼状B_nH_n~(2-)、CB_(n-1)H_n~-和C_2B_(n-2)H_n的硼氧团簇

笼状硼氢化合物BnHn2-、CBn-1Hn-和C2Bn-2Hn(n=5~12)含n个顶点和(n+1)对骨架电子,具有典型的三维芳香性、高的芳香化能和类似于苯的化学反应性.2005年以来,在研究B-O二元团簇的过程中,我们首次提出硼的硼羰基化合物(boron boronyls)和碳的硼羰基化合物(carbon boronyls)的概念,探讨了Bn(BO)m0/-1/-2(n=1~2,m=2~4)及Cn(BO)n(n=3~7)系列化合物的几何结构和电子性质.基于高分辨光电子能谱实验和密度泛函理论分析,确认线性B(BO)20/-1及三角形B(BO)30/-1新颖结构,首次发现线性D∞h B2(BO)22-离子含有B≡B三重键.理论和实验结合研究表明,BO与H具有等瓣相似性,BO自由基具有类似于CN的化学行为.在此基础上,本文用BO基团取代BnHn2-、CBn-1Hn-及C2Bn-2Hn(n=5~12)中的H原子,形成Bn(BO)n2-、CBn-1(BO)n-及C2Bn-2(BO)n(n=5~12)系列硼氧化物,对其几何和电子结构、稳定性和芳香性进行密度泛函B3LYP/6-311+G(3df)理论研究.图1给出n=1...     

亚磺化脱卤研究 VI.带极性取代基的伯碘代全氟烷的亚磺化脱碘

本文研究了取代基对亚磺化脱碘反应的影响,带极性取代基的碘代全氟烷I(CF~2)~nO(CF~2)~2-SO~3Na(1a～1c, n=2,4,6)、I(CF~2)~nOCF~2CO~2Na(2a～2b,n=2,4)、I(CF~2)~2O(CF2)2SO~2K(3)及I(CF~2)~4OCF~2CONH~2(4)于水溶液中在温和条件下可与连二亚硫酸钠进行亚磺化脱碘反应,生成相应取代的全氟烷基亚磺酸盐NaO~2(CF~2)~nSO~3O(CF2)2Na(5a～5c,n=2,4,6)、NaO~2S(CF~2)~2-OCF~2CO~2Na(6a～6b,n=2,4)、NaO~2S(CF~2)~2O(CF~2)~2SO~2K(7)及NaO~2(CF~2)~4OCF~2CONH2(8).这些亚磺酸盐均可按常规方法转化成相应取代的磺酰氯,从而提供了合成带这些取代基的全氟烷基亚磺酸盐及磺酸等衍生物的方便途径。     

碱金属原子吸附PPV及其衍生物体系的结构和非线性光学性质的理论研究

采用密度泛函理论(DFT)方法系统研究了碱金属Li原子吸附亚苯基-1,2-亚乙烯基(Phenylenevinylene)聚合物(PPV)及其衍生物(具有给受体基团修饰的)体系的结构和非线性光学性质.Li原子能稳定地吸附在PPV及其衍生物的表面,吸附能高达62.3~78.2 kJ/mol.当碱金属Li原子吸附在[PPV]n(n=2~4)表面时,锂盐效应导致了Li原子和[PPV]n之间发生了明显的电荷转移过程,使体系的一阶超极化率β0从249~756 a.u.明显增加到1.16×104~1.37×105a.u..当碱金属Li原子吸附在只有给体(—NH2)或只有受体(—CN)基团修饰的PPV衍生物{[NH2-(PPV)n]/[(PPV)n-CN]}时,体系的一阶超极化率值进一步提升,分别高达1.61×105a.u.(n=4)和2.85×105a.u.(n=4).这主要源于锂盐效应和Donor-π-Acceptor之间的协同作用导致跃迁能进一步降低所致.在Li原子吸附的具有给受体基团同时修饰的PPV衍生物(Li@[NH2-(PPV)n-CN])体系中,这种协同作用得到进一步加强,显著改善了体系的一阶超极化率(高达3.56×105a.u.,n=4).     

二核铪氧簇Hf_2O_n~(–/0)(n=1～6)的电子性质与结构演化的理论研究

采用密度泛函理论(DFT)与耦合簇[CCSD(T)]相结合的计算方法对一系列二核铪氧簇合物Hf_2O_n~(–/0)(n=1~6)的电子结构进行了系统研究.通过密度泛函理论(DFT)计算对体系的势能面进行广泛的搜索,寻找能量最低的结构.采用广义Koopmans定理计算垂直电子逸出能(VDEs)并模拟阴离子光电子谱(PES).通过理论研究阐明了二核铪氧簇Hf_2O_n~(–/0)(n=1~6)结构演化规律,并利用分子轨道分析对二核铪氧簇Hf2On–(n=1~4)的化学成键和顺序氧化进行解释.自旋密度分析显示:除Hf_2O_5中性簇之外,其它富氧簇都存在多种类型的氧自由基:氧自由基、双自由基或超氧自由基.此外,研究发现Hf2O3中性簇中的定域Hf2+位容易与分子氧O2反应形成Hf_2O_5中性簇;Hf_2O_4~(–/0)簇合物与分子O_2作用形成Hf_2O_6~(–/0)簇合物,Hf_2O_4~(–/0)簇合物可以作为潜在的分子模型研究氧分子在铪氧化物上的活化.     

含烯烃配体的过渡金属卡宾配合物的研究 Ⅱ.异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物的合成、波谱和结构研究及四羰基[乙氧基(五氯苯基)卡宾]铁的晶体结构

异戊二烯三羰基铁(1)与芳基锂ArLi(Ar=C_6H_5,p-CH_3C_6H_4,p-CH_3OC_6H_4,p-CF_3C_6H_4)在低温下反应,再用Et_3OBF_4烷基化,可获得组成为C_5H_8(CO)_2FeC(OC_2H_5)Ar的标题化合物的异构化产物(2—5).当用LiC_6Cl_5作亲核试剂,在相同条件下与1反应时,只生成已知的配合物(CO)_4FeC(OC_2H_5)C_6cl_5(6).由单晶X射线衍射数据推断出,2和6的分子结构都属于单斜晶系,Z=4.2的空间群为C_(2h)~5-P_2(1/n),α=8.544(2),b=14.494(5),c=12.309(4)A,β=96.16(2)°;6的空间群为C_(2h)~5-P2_(1/c),a=14.126(3),b=6.805(1),c=19.182(5)A,β=103.58(2)°.2和6的结构用SHELXTL直接法程序解出并经块矩阵最小二乘法修正,R分别为0.066和0.043.     

Ln(ClO~4)~3-PCBAAP-H~2O系统在30℃时的溶解度研究

测定了两个三元系统Ln(ClO~4)~3-PCBAAP-H~2O(Ln=La,Yb;PCBAAP：4-(对氯苯酰基)氨基安替比林,C~1~8H~1~6O~2N~3Cl)在30℃时的溶解度,发现两系统各有一个组成为Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Yb,n=2)的不一致溶解化合物生成。参考系统的溶解度研究结果,合成了系列化合物Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Pr,Nd,Sm,Gd,Yb,n=2),通过化学分析及元素分析,IR光谱,TG-DTG,XRD和密度测定对其进行了表征。     

金属离子与卟啉的嵌入反应动力学研究 IV.Cu(Ⅱ)T_(β-N-EAES)PyP~(4+)生成反应中的动力学盐效应

在不同离子强度的高氯酸钠水溶液中,用分光光度法测量自由卟啉H_2T_(β-N-EAES)PyPBr_4(简记为H_2P~(4+))与Gu(Ⅱ)离子的配位反应动力学,探讨高氯酸钠对Cu(Ⅱ)离子嵌入自由卟啉反应的催化本质.在给定条件下,高氯酸根与自由卟啉的缔合数n为1;缔合平衡常数K_0=3.70±0.42dm~3.mol~(-1).配位反应实验动力学方程为d[Cu(Ⅱ)P~(4+)]/dt=5.55×10~5γCu~2+γH_2P~4+γ(3)[ClO_4~-]~3[Cu~(2+)][H_2P]_总/(1.00+10~(2.02{H+}+10~(4.36{H~+}~2)、反应的活化能E=53.30kJ·mol~(-1),活化焓变△H~ =50.31kJ·mol~(-1),活化熵变△S~ =-77.65J·mol~(-1)·K~(-1).提出了金属卟啉生成反应中的ClO_4~-催化卟啉环变形的反应机理.     

氟烷基化和氟烷氧基化的研究8.钯(O)催化氟烷基碘对炔烃的加成反应

四(三苯基膦)钯(O)在温和的条件下能催化氟烷基碘R~FI[R~F=(CF~2)~nCl,n=2;n=4;n=6;R~F=(CF~3)~nCF~3;n=3;n=1;R~F=H(CF~2)~4]对炔烃(CH≡CC~4H~9,CH≡CSiMe~3,CH≡CPh)加成生成较高产率的加成产物.二(三苯基膦)二氯化肥(II)和二(三苯基膦)氟烷基碘化钯(II)在同样的条件下无催化作用.2,2-硝基,亚硝基丙烷能部分阻止反应,这表明反应的可能中间体是自由基,而不是二(三苯基膦)氟烷基碘化钯(II).     

氟氯代β-二酮镧系合物的合成以及作为位移试剂的研究

合成了一些氟氯代β-二酮镧系螯合物(CF2ClCOCHCOR)3Ln.nH2O(2,Ln=Eu:2a,R=C(CH3)3,n=O;2b,R=C6F5,n=0;2c,R=CF2Cl,n=2.3,Ln=Pr:3a,R=C(CH3)3,n=0;3b,R=C6F5,n=1;3c,R=CF2Cl,n=2.4,Ln=La,R=C6H5,n=0).测试了化合物2和3的位移性能,其中2的位移性能与Eu(fod)3相近,而2b,2c,3b和3c则由于本身没有1H峰,故性能优于Eu(fod)3.化合物2和3易溶于CHCl3和CCl4等非极性有机溶剂。     

ESR SPECTRA OF VO(NCS)_n~((2-n) ) COMPLEXES AND DETERMINATION OF THEIR STABILITY CONSTANTS

The ESR spectra of VO(NCS)_n~((2-n) ) complexes have been studied in this paper. It is shown that four complexes ions of various compositions, VO(NCS)~ , VO(NCS)_2, VO(NCS)_3~- and VO(NCS)_4~(2-), are formed in glyeol-water-mixed media. The parameters of the ESR spectra have been determined. We established a linear correlation between the hyperfine coupling constant and the coordination number n. n=117.66-3.41n (gauss). All the stability constants for various complexes formulated as VO(NCS)_n~((2-n) )(n=1,2,3,4) have been calculated from the ESR spectra, log K_1=2.15; log K_2=1.55; log K_3=0.87; log K_4=0.22. K_3and K_4 have not been reported in literature up to now.     

μ-O-二[(全甲基多硅撑)二环戊二烯基氯络锆]的合成与结构

将α,ω-二氯全甲基多硅烷相继与环戊二烯基钠、正丁基锂及四氯化锆作用,生成的全甲基多硅撑桥连二环戊二烯基二氯化锆(Me_2Si)_n(C_5H_4)_2 ZrCl_2(n=2,3)在碱性条件下被水解,生成标题化合物[(Me_2Si)_n(C_5H_4)ZrCl]_2O.用元素分析、~1HNMR和质谱表征了其结构,进而对两个化合物的单晶进行X射线结构分析,确证其分子结构.n=2的晶体属P2_1/C空间群,晶胞参数a=14.268(4),b=7.812(1),c=31.050(5)A;β=99.59°;Z=4.最终偏差因子R=0.039.n=3的晶体属C_2空间群,晶胞参数a=19.944(1),b=17.117(1),c=15.966(1)A;β=128.68°;Z=4.最终偏差因子R=0.033.最后讨论了硅桥对配合物分子结构及性质的影响.     

Syntheses,Crystal Structures,DFT Calculation and Optical Properties of a Schiff Base and Its Dinuclear Mercury(Ⅱ) Complex

A pyridine-contained Schiff base ligand L(L =(pyridine-2-vinyl)hydrazine) has been synthesized and fully characterized. By self-assembly of the ligand with HgI_2, a binuclear complex Hg_2I_4L(C) was obtained. The structures of L and C were analyzed through single-crystal X-ray diffraction. L crystallizes in monoclinic, space group P21/n with a=11.286(5), b=3.981(5), c=23.865(5) ?, β=100.043(5)°, V=1056(1) ?~3, Z=4, Dc=1.323 g/m~3, F(000)=440, Μr=210.24, μ=0.084 mm~(-1), the final R=0.0928 and w R=0.2867 for 6955 observed reflections with I 2(I). The complex is of monoclinic system, space group P21/n with a=8.706(5), b=17.468(5), c=14.675(5) ?, β=93.922(5)°, V=2227(2) ?~3, Z=4, Dc=3.338 g/m~3, F(000)=1928, Μr=1119.02, μ=19.321 mm~(-1), the final R=0.0366 and w R=0.1276 for 3920 observed reflections with I 2(I). The structural analysis revealed that the molecule of L possesses a well planar structure. However, in the complex, the coordinated ligand distorts greatly. The absorption spectra of L and the complex in ethanol were experimentally and theoretically studied. The result indicates that the complex exhibits different absorption spectrum compared with the free ligand.     

苯并-15-冠-5四溴合铟酸钾配合物的晶体结构

苯并-15-冠-5-四溴合铟(III)酸钾,KInBr~4(C~14H~20O~5)~2,晶体属单斜晶系,空间群为C~2h^5-P2~1/n,晶胞参数a=14.402(3),b=15.082(3),c=17.262(5)A,β=93.42(2),Z=4.非氢原子的位置由Patterson函数及Fourier合成法找出,经全矩阵最小二乘法修正R=0.057.结构分析表明K^+和两个苯并-15-冠-5(B-15-C-5)分子直接配位,对阴离子为InBr~4^-,具有四面体构型.InBr~4^-与配阳离子K(B-15-C-5)~2^+依靠静电引力结合为离子对.由此说明,In(III)在过量KBr存在下可以被B-15-C-5定量地萃取至有机相中.     

链式多Li掺杂分子H(HC==N-Li)nH(n=1~6)的NLO性质及链长依赖性

对链式多Li掺杂体系H(HCN-Li)_nH(n=1~6)的结构与性质进行了研究. 发现随着链长n的增大, 体系中有两类分子出现. 当n=1, 2时, 由于额外电子轨道是空的, 从而形成了Li 盐分子; 而当n=3~6时, 额外电子轨道是占据的, 从而形成了具有大范围额外电子云的多Li电子化物分子. 对于系列体系H(HCN-Li)_nH(n=1~6), 其非线性光学(NLO)性质的依赖性呈现阶梯式增长的规律, 即静态第一超极化率β₀的次序为2179, 2776(n=1, 2)< 5492, 5487(n=3, 4)< 15235, 15377(n=5, 6), 表明增加Li原子掺杂数是提高NLO响应的新途径.