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A STUDY OF NEW RHODIUM COMPLEX WITH CARBORANE LIGAND
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作者 郑利民 邝冠南 陆健 《Journal of Donghua University(English Edition)》 EI CAS 1989年第Z1期125-130,共6页
The complex [closo-3,3-(PPh<sub>3</sub>)<sub>2</sub>-3-H-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]has a rich derivative chemistrythat is currently ... The complex [closo-3,3-(PPh<sub>3</sub>)<sub>2</sub>-3-H-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]has a rich derivative chemistrythat is currently under active investigation.The resultant compound shows an increasing stabilitythat is often associated with metallocarboranes.This paper deals with the novel and the produc-tion area of carborane complexes of transition metals.The paper indicates that some reactions can easily proceed and the resulting compound hassome new properties and uses.K[18-crown-6][closo-3-Ph<sub>3</sub>P-3-CH<sub>2</sub>Ph-3-Br-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]can be synthesized by the reaction of K[18-crown-6][(Ph<sub>3</sub>P)<sub>2</sub>RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]withbromo-toluene under the condition of dry benzene.IR and <sup>1</sup>H,<sup>11</sup>B,<sup>31</sup>p nuclear magnetic reso-nance and elemental analysis comfirm the structure for this species with one carborane groupbonded to the central metal. 展开更多
关键词 Synthesis transition ELEMENT carboraneS LIGANDS ICOSAHEDRON metallocarborane
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Synthesis, Structure and Characterization of a Novel Asymmetrical Half-sandwich Binuclear Iron Carborane Complex [η5-C5H3(t-Bu)2]2Fe2(CO)3Se2C2B10H10
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作者 LU Shi-xiang JIN Guo-xin +1 位作者 HU Ning-hai JIA Heng-qing 《Chemical Research in Chinese Universities》 SCIE CAS CSCD 2002年第4期405-408,共4页
Halfsandwich iron dicarbonyl complex [η 5-C5H3(t-Bu)2]Fe(CO)2Cl(1) reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10(2) to give a binuclear iron carborane complex [η 5-C5H3(t-Bu)2]2Fe2(CO)3&... Halfsandwich iron dicarbonyl complex [η 5-C5H3(t-Bu)2]Fe(CO)2Cl(1) reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10(2) to give a binuclear iron carborane complex [η 5-C5H3(t-Bu)2]2Fe2(CO)3·Se2C2B 10H 10(3). The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral. 展开更多
关键词 carborane Halfsandwich iron complex CHIRALITY Molecular structure
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Synthesis and Crystal Structure of a B-H Activated Compound Containing a Furan Ring and an ortho-Carborane Cage
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作者 叶红德 胡久荣 +4 位作者 郑大贵 彭化南 叶青 部如意 燕红 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2013年第10期1517-1522,共6页
A new compound [CpCo(Se2C2BIoH9)CH2C(O)C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic... A new compound [CpCo(Se2C2BIoH9)CH2C(O)C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481(10), b = 24.6600(12), c = 25.7430(14) A, β = 100.863(3)°, C42H57B30Co306Se6"CH2C12"0.25H20, Mr = 1722.16, V = 6825.6(8) A3, Dc= 1.676 g/cm3, Z = 1 and F(000) = 3346. The molecular structure shows a 1:1 ratio product of the two reactants of 16e half-sandwich complex CpCo(Se2C2B10H10) and alkyne 1-(2-furyl)-2-propyn-l-one. The hydrogen atom in the B(3) position of CpCo(Se2C2B10HIo) has been activated and migrated to the terminal carbon of 1-(2-furyl)- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds. 展开更多
关键词 carborane ALKYNE B-H activated crystal structure
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Visible-Light-Promoted Palladium-Catalyzed Cross-Coupling of lodocarboranes with Disulfides and Phenylselenyl Chloride
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作者 Shimeng Li Yizhen Liu Zuowei Xie 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2024年第2期129-134,共6页
This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron-centered carbora... This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron-centered carboranyl radicals.Such hypervalent boron radicals are generated by a visible-light-promoted Pd(O)/Pd(I)pathway.They are useful intermediates and can be trapped by disulfides and phenylselenyl chloride for the convenient construction of B-S/Sebonds. 展开更多
关键词 carborane SULFENYLATION Selenylation B-I activation RADICAL Photocatalysis Boron SELECTIVITY
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Superatom-assembled boranes,carboranes,and low-dimensional boron nanomaterials based on aromatic icosahedral B_(12)and C_(2)B_(10)
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作者 Qiao-Qiao Yan Yan-Fang Wei +2 位作者 Qiang Chen Yue-Wen Mu Si-Dian Li 《Nano Research》 SCIE EI CSCD 2024年第7期6734-6740,共7页
Using the experimentally known aromatic icosahedral superatoms I_(h)B_(12)H_(12)2−and D_(5d)1,12-C_(2)B_(10)H_(12)as building blocks and based on extensive density functional theory calculations,we predict herein a se... Using the experimentally known aromatic icosahedral superatoms I_(h)B_(12)H_(12)2−and D_(5d)1,12-C_(2)B_(10)H_(12)as building blocks and based on extensive density functional theory calculations,we predict herein a series of core–shell superpolyhedral boranes and carboranes in a bottom-up approach,including the high-symmetry Th B_(12)@B_(152)H_(72)2−(2),C2h C_(2)B_(10)@B_(152)H_(72)(3),D_(3d)B_(12)@B_(144)H_(66)(4),I_(h)B_(12)@C_(24)B_(12)0H_(72)2−(6),and D_(5d)C_(2)B_(10)@C_(24)B_(12)0H_(72)(7).More interestingly,the superatom-assembled linear D2h B_(36)H_(32)^(2−)(8),close-packed planar D_(3d)B_(84)H_(60)^(2−)(10),and nearly close-packed core−shell D_(3d)B_(12)@B144H_(6)6(4)can be extended periodically to form the one-dimensional(1D)α-rhombohedral borane nanowire B_(12)H_(10)(Pmmm)(9),two-dimensional(2D)α-rhombohedral monolayer borophane B_(12)H_(6)(P m1)(11),and the experimentally known three-dimensional(3D)α-rhombohedral boron(R m)(12)which can be viewed as an assembly of the monolayer B_(12)H_(6)(11)staggered in vertical direction,setting up a bottom-up strategy to form low-dimensional boron-based nanomaterials from their borane“seeds”via partial or complete dehydrogenations.Detailed bonding analyses indicate that the high stability of these nanostructures originates from the spherical aromaticity of their icosahedral B_(12)or C_(2)B_(10)structural units which possess the universal skeleton electronic configuration of 1S21P61D101F8 following the Wade’s n+1 rule.The infrared(IR)and Raman spectra of the most-concerned neutral B_(12)@B144H_(6)6(4)and C_(2)B_(10)@C_(24)B_(12)0H_(72)(7)are computationally simulated to facilitate their experimental characterizations. 展开更多
关键词 superatom-assembling bottom-up approach density functional theory superpolyhedral boranes superpolyhedral carboranes borophanes
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Nickel-catalyzed regioselective B(3,4,5,6)-H tetra-alkylation of o-carboranes
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作者 Jianwei Zhao Zuowei Xie 《Science China Chemistry》 SCIE EI CAS CSCD 2023年第10期2836-2841,共6页
Though transition metal-catalyzed cage BH methylation has been well documented, catalytic alkylation of cage BH bonds remained elusive because transition metal alkyl complexes are prone to undergo β-H elimination. We... Though transition metal-catalyzed cage BH methylation has been well documented, catalytic alkylation of cage BH bonds remained elusive because transition metal alkyl complexes are prone to undergo β-H elimination. We report herein a highly efficient 8-aminoquinoline-assisted nickel-catalyzed regioselective cage B(3,4,5,6)-H tetra-alkylation of o-carboranes employing unactivated alkyl bromides as alkylating agents in the absence of any oxidants, leading to the preparation of a class of tetra-alkylated o-carboranes with a broad substrate scope in good to very high yields. This method opens new avenues for oxidant-free, direct, efficient, sustainable, and regioselective multiple B–H alkylation of carboranes via base metal catalysis. 展开更多
关键词 nickel catalysis B-H activation carborane ALKYLATION regioselectivity
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Octanuclear Palladacycles with B(3)-H Bond Activation of o-Carborane
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作者 Run-Ze Yuan Peng-Fei Cui +1 位作者 Yue-Jian Lin Guo-Xin Jin 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2023年第3期307-313,共7页
Herein,we describe the synthesis of a carborane-supported octanuclear palladacycle complex,Pd_(8)(o-C_(2)B_(10)H_(10)CS_(2)CH_(3))_(4)Cl_(4)(CH_(3)CN)_(4)(complex 1),with B(3)-H activations on o-carborane ligand.The s... Herein,we describe the synthesis of a carborane-supported octanuclear palladacycle complex,Pd_(8)(o-C_(2)B_(10)H_(10)CS_(2)CH_(3))_(4)Cl_(4)(CH_(3)CN)_(4)(complex 1),with B(3)-H activations on o-carborane ligand.The substitution reaction of 1 has been explored,and three of its substituted complexes Pd_(8)(o-C_(2)B_(10)H_(10)CS_(2)CH_(3))_(4)Cl_(4)(L)4(L=^(t)BuNC,2;L=C_(5)H_(5)N,3;L=C_(4)H_(8)S,4)have been synthesized.The m-and p-carborane disubstituted ligands m-and p-C_(2)B_(10)H_(10)(CS_(2)CH_(3))_(2)(ligands 5 and 6)as well as their B—H activated carborane complexes[m-C_(2)B_(10)H_(9)(CS_(2)CH_(3))_(2)PdCl](7)and[p-C_(2)B_(10)H_(8)(CS_(2)CH_(3))_(2)][PdCl(^(t)BuNC)]_(2)(8)have also been synthesized by the similar method.All of these complexes have been characterized,including X-ray single crystal diffraction,NMR spectroscopy,IR spectroscopy and elemental analysis methods. 展开更多
关键词 carborane Palladacycle Regioselective B-H activation Polynuclear complex Dithioester chemistry
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N-Heterocyclic Carbenes with a Nido-C_(2)B_(9) Carborane Backbone 被引量:1
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作者 Zhongzheng Cui Beining Wang +3 位作者 Junxia Li Ronglin Pang Yanrui Kang Xu-Qiong Xiao 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2021年第9期2410-2416,共7页
The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by ... The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by the changes of the backbones.Herein,we report the usage of nido-C_(2)B_(3) carbora ne anions as the backb ones of NHCs.Stirring the mixture of sec on dary amino o-carbora nes(lb-le),triethyl orthoformate and HBF4-Et2O results in the unexpected cage-opening of o-carboranes to afford the n/do-C_(2)B_(9) carbora ne anions supported A/-heterocyclic carbene precursors(4b-4e).Deprotonation of 4b with sodium hexamethyldisilazide at-78℃ affords the/V-heterocyclic carbene ligand,which was used to form an Au(I)NHC complex(5).DFT calculations revealed a high-lying lone pair orbitals of the carbene ligands,predicting their strong o-donating abilities. 展开更多
关键词 carboraneS nido-carborane anion Carbene ligands Density functional calculations Gold
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On Desilylation of 13-Vertex Carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)
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作者 Jian Zhang Zuowei Xie 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2014年第8期777-782,共6页
The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH... The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH_(2)-linkage have been prepared and structurally characterized for comparison.Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C_(4)Si ring,Lewis acidity of Si atom and Brønsted acidity of silica surface. 展开更多
关键词 cage compounds carboraneS cluster compounds DESILYLATION ruthenacarboranes
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Copper catalyzed/mediated direct B–H alkenylation/alkynylation in carboranes 被引量:2
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作者 Yu Chen Yik Ki Au +1 位作者 Yangjian Quan Zuowei Xie 《Science China Chemistry》 SCIE EI CAS CSCD 2019年第1期74-79,共6页
Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords ... Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate. 展开更多
关键词 [4+2] annulation ALKYNYLATION B-H activation base metal catalysis carborane
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Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties 被引量:5
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作者 Ning Li Fang-Lei Zeng +5 位作者 Yu Wang De-Zhi Qu Chun Zhang Juan Li Jin-Zhao Huo Yong-Ping Bai 《Chinese Journal of Polymer Science》 SCIE CAS CSCD 2018年第1期85-97,共13页
In this study, two fluorinated polyurethanes(FPU) containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer(HDI trimer) with fluorin... In this study, two fluorinated polyurethanes(FPU) containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer(HDI trimer) with fluorinated polyesters(CFPETs) having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters(CFPETs) and polyurethanes(CFPUs) were characterized by gel permeation chromatography(GPC), Fourier transform infrared(FTIR) spectroscopy and nuclear magnetic resonance(NMR) measurements. The thermal stability, mechanical properties, Shore A hardness, solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis(TGA) tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane(CFPU) increased by 190 °C compared with that of the carborane-free fluorinated polyurethane(FPU). Even at 800 °C, CFPU showed the char yield of 66.5%, which was higher than that of FPU(34.3%). The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature(700 °C). It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability, mechanical property, solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines, engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments. 展开更多
关键词 Fluorinated polyurethane carborane Thermal stability Mechanical property Chemical resistance
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Synthesis of carborane-fused cyclobutenes and cyclobutanes 被引量:1
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作者 YUAN YingGen REN ShiKuo +2 位作者 QIU ZaoZao WANG ShaoWu XIE ZuoWei 《Science China Chemistry》 SCIE EI CAS 2014年第8期1157-1163,共7页
Transmetalation of carborane-fused zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carb... Transmetalation of carborane-fused zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu(II) and reductive elimination is proposed. 展开更多
关键词 carborane CYCLOBUTENE CYCLOBUTANE zirconacycle copper
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Reaction of o-Carboryne with Furans: Facile Synthesis of Carborane- Fused Oxanorbornenes and Their Derivatives 被引量:1
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作者 RongyiZhang Yinggen Yuan +1 位作者 Zaozao Qiu Zuowei Xie 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2018年第4期273-279,共7页
o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused o... o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4+2]/[2+2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science. 展开更多
关键词 carborane carboryne [4+2] cycloaddition FURAN ring opening reaction
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Synthesis, Characterization and Thermal Stability of Novel Carborane- Containing Epoxy Novolacs 被引量:1
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作者 guo han zhen yang +3 位作者 xiao-xue yang 张孝阿 sheng-ling jiang ya-fei lu 《Chinese Journal of Polymer Science》 SCIE CAS CSCD 2016年第9期1103-1116,共14页
Carborane bisphenol novolacs (3 and 4) were synthesized in the presence of acid catalyst from carborane bisphenols (5 and 6) and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohy... Carborane bisphenol novolacs (3 and 4) were synthesized in the presence of acid catalyst from carborane bisphenols (5 and 6) and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohydrin gave carborane bisphenol epoxy novolacs (1 and 2). The molecular weight and epoxy value of obtained resins were determined using the molecular weight of their precursors. The epoxy values of 1 and 2 were 0.48 and 0.52 respectively, higher than the maximum theoretical epoxy value (0.45) of difunctional carborane bisphenol epoxy resins. FTIR and NMR were utilized to characterize 1 and 2. The curing behaviors were also studied by DSC and the optimized curing conditions were obtained. TGA analysis indicated that carborane moiety could shield its adjacent organic structures against initial decomposition. On the other hand, B--H on carborane cage could react with oxygen to form a three-dimensional network linked by B--O--B and B--C bonds, which further blocked the movement of formed radicals and thus the degradation process was inhibited. 展开更多
关键词 carborane Epoxy novolacs Thermal stability.
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Synthesis and Characterization of Carborane-containing Poly(hydroxy ethers) with Excellent Thermal Stability 被引量:1
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作者 Zhen Yang Ning Li +3 位作者 Xiao-xue Yang 张孝阿 Sheng-ling Jiang Ya-fei Lyu 《Chinese Journal of Polymer Science》 SCIE CAS CSCD 2017年第12期1463-1473,共11页
o-Carborane-containing poly(hydroxy ethers)(P1, P2 and P3) were synthesized via "advancement reaction" of o-carborane-containing bisphenol(4) and diglycidyl ether of bisphenols(DGEBA and 1). FTIR and 1^H^-,... o-Carborane-containing poly(hydroxy ethers)(P1, P2 and P3) were synthesized via "advancement reaction" of o-carborane-containing bisphenol(4) and diglycidyl ether of bisphenols(DGEBA and 1). FTIR and 1^H^-, 13^C^-, and 11^ B-NMR were utilized to characterize the obtained polymers. TGA test was conducted under nitrogen and air. It is found that the shielding effect of carborane moiety on its adjacent aromatic structures contributes to high initial decomposition temperatures, while oxygen in air has an adverse effect on the initial decomposition temperature. The oxygen can combine with polymer chain to form peroxide and hydroperoxide groups, which are more reactive during the degradation process. Besides, o-carborane-containing poly(hydroxy ethers) have high char yield at elevated temperatures. The boron atom combines with oxygen from the polymer structure or/and from air, thus to form a three-dimensional network linked with B―O―B and B―C bonds, and retain the polymer weight to a large extent. 展开更多
关键词 carborane Poly(hydroxy ethers) Thermal stability
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Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand 被引量:1
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作者 HU Ping LI ZhenHua JIN GuoXin 《Science China Chemistry》 SCIE EI CAS 2014年第8期1137-1143,共7页
Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=tBu] was synthesized by the reaction of CpZrCl3(Cp=η5-C5H5) with sodium salt of ligand 2.... Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=tBu] was synthesized by the reaction of CpZrCl3(Cp=η5-C5H5) with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane(MAO), complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins. 展开更多
关键词 half-sandwich zirconium complex ethylene (co-)polymerization carborane ligand
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Study on specific interaction of new ferrocene-substituted carborane conjugates with hemoglobin protein 被引量:1
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作者 WU ChunHui1,3, YE HongDe2, JIANG Hui1, WANG XueMei1 & YAN Hong2 1State Key Lab of Bioelectronics (Chien-Shiung Wu Lab), Southeast University, Nanjing 210096, China 2State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China 3School of Life Science and Technology, University of Electronic Science and Technology of China, Chengdu 610054, China 《Science China Chemistry》 SCIE EI CAS 2012年第4期594-603,共10页
The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates (denoted as FcSB1, FcSB2 and FcSBCO) and hemoglobin (Hb) are investigated by electrochemistry, fluorescen... The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates (denoted as FcSB1, FcSB2 and FcSBCO) and hemoglobin (Hb) are investigated by electrochemistry, fluorescence and UVvis absorption spectroscopy. The results demonstrate that FcSB1, FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms, inducing the allosteric change from the R state (oxygenated conformation, relax) to T state (deoxygenated conformation, tense). The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1. Moreover, the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb. Typically, FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb. Such distinct influences are attributed to the structural features of FcSB1, FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group. Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs. 展开更多
关键词 fluorescence UV vis absorption spectroscopy differential pulse voltammetry biomolecular interaction ferrocene substituted carborane conjugates hemoglobin
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Comparison of luminescent properties of helicene-like bibenzothiophenes with o-carborane and 5,6-dicarba-nidodecaborane 被引量:1
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作者 Kenta Nishino Kazushi Hashimoto +2 位作者 Kazuo Tanaka Yasuhiro Morisaki Yoshiki Chujo 《Science China Chemistry》 SCIE EI CAS CSCD 2018年第8期940-946,共7页
This article describes comparison of the anchoring effect on electronic properties of the helicene-like bibenzothiophene between o-carborane and 5,6-dicarba-nido-decaborane. The o-carborane and nido-decaborane-fused b... This article describes comparison of the anchoring effect on electronic properties of the helicene-like bibenzothiophene between o-carborane and 5,6-dicarba-nido-decaborane. The o-carborane and nido-decaborane-fused bibenzothiophenes were simultaneously obtained in the same reaction and successfully isolated. Initially, the X-ray single crystal analysis revealed that the helicene-like distorted structure was realized in the nido-decaborane-fused bibenzothiophene. From optical measurements in the solution state, distinct different characteristics depending on the type of anchors were observed. It was summarized that the absorption and luminescent properties originated from weak π-conjugation at the bibenzothiophene moiety in the o-carboranefused compound were obtained, whereas robust π-conjugation and significant emission from the intramolecular charge transfer state were detected from the nido-decaborane-fused compound. These data can be explained by the theoretical results that π-conjugation was restrictedly developed within the bibenzothiophene moiety in frontier orbitals of the o-carborane-fused compound. In contrast, π-conjugation can be constructed even through the distorted bibenzothiophene because of the nido-decaborane unit. Moreover, the intramolecular charge transfer state should be realized because of electronic interaction involving the nido-decaborane unit in the excited state. Furthermore, it was demonstrated that the nido-decaborane-fused compound possessed solid-state emission and mechanochromic luminescent properties. The π-conjugation on the distorted structure supported by the nido-decaborane anchor should play a significant role in suppressing aggregation-caused quenching followed by presenting solid-state emission with stimuli responsiveness. 展开更多
关键词 carborane helicene mechanochromism aggregation-induced emission
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Regioselective B—H/C—H Bond Activation at Azo-Substituted Carboranes Induced by Half-Sandwich Iridium(III)Complex
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作者 Peng-Fei Cui Yang Gao +1 位作者 Shu-Ting Guo Guo-Xin Jin 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2021年第2期281-287,共7页
We report herein a practical approach for regio-selective B—H/C—H bond activation at azo-substituted carboranes. The reaction proceeded through Iridium(III)-induced selective B—H/C—H bond activations based on an a... We report herein a practical approach for regio-selective B—H/C—H bond activation at azo-substituted carboranes. The reaction proceeded through Iridium(III)-induced selective B—H/C—H bond activations based on an azo directing group. Through this strategy, a series of mononuclear, trinuclear and tetranuclear cyclometalated iridium complexes containing Cp*Ir—B or Cp*Ir—C bonds were successfully isolated in a high yield. In this work, efficient routes are developed through one-pot reactions to prepare polynuclear organometallic complexes. 展开更多
关键词 carborane B-H bond activation HALF-SANDWICH IRIDIUM POLYNUCLEAR
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Recent advances on carborane-based ligands in low-valent group 13 and group 14 elements chemistry
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作者 Hao Wang 《Chinese Chemical Letters》 SCIE CAS CSCD 2022年第8期3672-3680,共9页
Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabiliti... Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review. 展开更多
关键词 carborane Borylene CARBENE SILYLENE Main group chemistry
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