Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion

Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC₆H₄)-closo-1,2-C₂B₁₀H₁₀-2-)₂(4-MeC₆H₄)B] ( 1 ), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr₂. Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1^.− was isolated and characterized. Single-crystal structure analyses allow an in-depth comparison of 1 , 1^.− , their calculated geometries, and the S₁ excited state of 1 . Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD-DFT calculations were used to identify transition-relevant orbitals.     

Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring-Opening Polymerization to Give Polymers with Low Molecular Weight Distribution

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (Đ) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low Đ are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3–3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low Đ and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.     

Synthesis and Characterization of Heterobimetallic Aluminum‐Germanium(IV) Disulfides

Three heterobimetallic aluminum‐germanium(IV) disulfides are synthesized. The reaction of {LAl[(SLi)₂(THF)₂]}₂ ( 1 ) (L = HC(CMeNAr)₂, Ar = 2,6‐iPr₂C₆H₃) with Ph₂GeCl₂, Me₂GeCl₂, and GeCl₄, respectively, in THF afforded LAl(μ‐S)₂GePh₂ ( 2 ), LAl(μ‐S)₂GeMe₂ ( 3 ) and LAl(μ‐S)₂Ge(μ‐S)₂AlL ( 4 ) in good yields. Compounds 2 , 3 and 4 were investigated by elemental analysis, NMR, EI‐MS and 3 was also characterized by single crystal X‐ray structural analysis.     

Synthesis of Five Coordinate Spirocyclic Germanium(IV) Complexes Containing Diethanol Amine

Reaction of dihydroxo(2,2′-iminodiethanolato-AWO′) germanium(IV) (A) or dihydroxo(2,2′-methyliminodiethanolato-N,O.O′) germanium(IV) (B) with bidentate ligands, e.g. diol, α-hydroxy acid, oxalic acid, 2,6-pyridinedicarboxylic acid, or 2-aminophenol in a mixture of ethanol and xylene mixture yielded a series of unsymmetrical spiro-germanium complexes 1-6. These complexes were characterized by NMR, IR, mass spectra and elementary analysis. The ¹H NMR spectrums of all these compounds show the existence of an intramolecular N – Ge bond. X-ray analysis of compound 6 shows a short N–Ge bond (2.08 Å).     

Electronic Characteristics of Perylene Diimide Anion Radical and Dianion Films by Quantitative Doping

Due to their unique physicochemical properties, the anion radical and dianion of perylene diimide derivatives(PDIs) recently attracted significant attention for organic semiconductors. However, the impact of packing structure and the radical content for carrier transport in the solid state still need to be determined. Bringing the electron-withdrawing groups is an effective strategy for enabling π-π stacking distance. Here, bay-tetrachloro-substituted PDI(B-4Cl-PDI) anion radical and dianion films were fabricated quantitatively doped with N₂H₄·H₂O. The radical contents were quantitatively calculated by absorption spectra in different doping ratios. The X-ray powder diffraction patterns showed that the anion radical presented a crystalline structure, and dianion aggregates exhibited an amorphous structure. With precise manipulation of the radical content, the anion radical aggregates and dianion aggregates showed the maximum electrical conductivity value of 0.024 and 0.0018 S/cm, respectively. The experiment results show that doping level and aggregate structure play a crucial role in electronic transport properties.     

The First Structural Characterization of an Azoaromatic Radical Anion Stabilized by Dicopper(I) Coordination

Double chelate coordination of [Cu(Ph₃P)₂]⁺ stabilizes the radical anion of 2,2′-azobis(5-chloropyrimidine), which exhibits a N–N bond length of 1.345(7) Å in the complex (see picture). This is consistent with a one-electron reduced azo functionality.     

The Effect of the Anion of the Salt Background of the Aqueous Phase on the Extraction of Germanium (IV) 8-Hydroxyquinolinate

Abstract

The effect of the anion of the salt background of the aqueous phase on the extraction of the 8-oxyquinolinate of germanium has been investigated The anion effect is associated with the change in ionization constants and distribution of 8-oxyquinoline The degree of anion influence depends on the reagent concentration.     

含双蒽基团酰胺受体分子的合成及阴离子识别研究

合成了一种新型的带有双蒽基团的酰胺阴离子受体B.用荧光光谱、紫外-可见吸收光谱以及核磁共振氢谱研究了B与Cl^-,Br^-,I^-及对硝基酚氧阴离子的相互作用.结果表明,B与Cl^-,Br^-,I^-等阴离子无识别作用,而与对硝基酚氧阴离子有较好的选择性识别能力,其络合比为1∶1.利用荧光发射强度和吸光度的变化分别计算出主体B与客体相互作用的络合常数KS分别为(1.24±0.07)×10⁵和(1.27±0.18)×10⁵,并对主体分子B与客体之间的相互作用进行了讨论.     

Reactions of Ru3(CO)12 with Diphosphenes — A New Route to 50‐Electron Ru3P2 nido‐Clusters

The reaction of the symmetric diphosphene 2, 4, 6‐(CF₃)₃‐C₆H₂‐P=P‐C₆H₂‐2, 4, 6‐(CF₃)₃ 4 with Ru₃(CO)₁₂ led to the 50‐electron Ru₃P₂ nido‐cluster Ru₃(CO)₉[μ‐P‐C₆H₂‐2, 4, 6‐(CF₃)₃]₂ 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru₃P₂ centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C₆H₂(CF₃)₃ groups is also appreciably distorted. Temperature‐dependent ¹⁹F NMR studies of the [A₃M₃X]₂ spin system (A = M = CF₃, X = ³¹P) of 5 indicated a rotational barrier ΔG^≠ of 82.3 kJ mol^‐1 at 141 °C. The same Ru₃P₂ core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru₃(CO)₁₂; hindered rotation about the C(aryl)—P bonds was also observed, in this case.     

Synthesis,Structure, and Radical Anion of the First Stable p‐Phosphaquinone

Significant localization of the unpaired electron on the phosphorus atom of phosphasemiquinone radical anion 1 was revealed by EPR spectroscopy. This species was generated by reduction of 1 , the first stable p‐phosphaquinone. Employment of the 3,5‐di‐tert‐butyl‐4‐oxocyclohexa‐2,5‐dien‐1‐ylidene moiety was essential for the synthesis as well as the effective kinetic protection of 1 .     

Facile Synthesis of Pentacarbonyltungsten(0) Complexes with Oxaphosphirane Ligands

Facile synthesis of tungsten(0) complexes of the type 7a – g (R¹ = C₅Me₅) and 8a – g (R¹ = CH(SiMe₃)₂) using transient Li/Cl phosphanylidenoid tungsten(0) complexes 4 , 5 and carbonyl derivatives 6a – g is reported; furthermore, for all complexes NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single‐crystal X‐ray structures of complexes 7b , d – g and 8b , d are presented.     

耐高温阴离子交换树脂的合成及在环氧乙烷催化水合反应中的应用

我们合成了一种新型结构的季铵型阴离子交换树脂催化剂(NC-1),并将其转型为碳酸氢根型应用于环氧乙烷(EO)催化水合反应.并用NC-1、D201树脂催化EO水合反应进行了考察.NC-1型离子交换树脂催化剂,因具有较好的热稳定性,其使用寿命比D201树脂提高到数十倍.同时,还设计了一种“二步法”新型水合工艺,与传统水合工艺相比,这种工艺有效地抑制了树脂催化剂的膨胀.在使用105h后,催化剂的膨胀率由原来的76%下降到5%左右.     

Anion dependent formation of Ag(I) complexes of multidentate azine ligands: Synthesis and structural study

The extended structures of Ag-complexes of the azine based ligands phenyl-2-pyridyl ketone azine (L₁) and di-2-pyridyl ketone azine (L₂) are reported, and focus is made on the investigation of the influence of the anion and supramolecular interactions on the self-assembly. Using AgNO₃, AgClO₄ and CF₃COOAg salts as starting materials for both ligands in acetonitrile, we observed the formation of the dinuclear complexes [Ag₂(L₁)₂](NO₃)₂ (1a), [Ag₂(L₁)₂](ClO₄)₂ (1b), from L₁, the tetranuclear complexes [Ag₄(L₂)₂ (NO₃)(CH₃CN)₂](NO₃)₃ (2a), [Ag₄(L₂)₂(CF₃COO)₃CH₃CN](CF₃COO) (2b) and the linear chain polynuclear complex {[Ag₃(L₂)₂] (ClO₄)₃}_n (3) from L₂. The X-ray structures show that the molecular geometry depends on the choice of anion. The silver centers have distorted tetrahedral coordination geometry in all the complexes. Weak hydrogen bonding and other interactions result in 2-D and 3-D networks in these complexes.     

以交联聚乙烯醇为载体的阴离子交换剂的合成与性能研究

大孔乙酸乙烯酯－异氰尿酸三烯丙酯共聚物树脂经醇解生成亲水性的交联聚乙烯醇，然后相继与环氧氯丙烷和二乙胺反应，合成出含二乙基氨基羟丙基的阴离子交换剂，研究了交联聚乙烯醇环氧基化的最佳条件，发现以二甲基亚砜作溶剂能够显著地提高活化程度，反应时间以３ｈ为最佳，并研究了该阴离子交换剂的交换量、亲水性、热稳定性、溶胀稳定性，发现它具备常压分离蛋白质所需的基本性能，是较为理想的生化用的离子交换剂。     

Synthesis of Poly （styrene-b-isoprene-b-styrene） via Nitroxide-mediated Radical Polymerization by a Novel Alkoxyamine

Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl （TIPNO） and α, ω-alkyl bromide by atom transfer radical addition（ATRA） was employed as “biradical initiator” for nitroxide-mediated radical polymerization（NMRP） of isoprene and styrene. The kinetics study for the polymerization of styrene at different time showed living features. The poly（styrene-b-isoprene-b-styrene） （SIS） copolymers have two glass transition temperatures, indicating the immiscibility of the corresponding blocks.     

Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2X (X=Br,I) and LaFI2

Mixed-anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF₃-LaX₃ (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF₂X and LaFX₂ (X=Br, I), which are respectively isostructural with LaHBr₂ and YH₂I, consisting of layered La-F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF₂Br and LaFI₂ crystallize in the predicted structure, while LaF₂I is similar to the predicted one but with different layer stacking. LaF₂I exhibits fluoride ion conductivity comparable to that of non-doped LaF₃, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed-anion compounds in future, in particular those with an ordered anion arrangement.     

C_（60）与n－Bu_3SnH的自由基反应研究

Ｃ_（６０）与ｎ－Ｂｕ_３ＳｎＨ的自由基反应研究余益民，郭兴华，刘子阳，刘淑莹，傅芳信，钱明星（中国科学院长春应用化学研究所，长春，１３００２２）（东北师范大学化学系）关键词自由基反应，富勒烯，三丁基锡氢化物，自由基海绵自Ｋｒａｔｓｃｈｍｅｒ等［１］实...