Reaction Chemistry of Osmapentalynes

金属卡宾、金属卡拜化合物是一类含有金属碳多重键的化合物。因其独特的 结构和性质，自发现以来就备受关注。2013年，本课题组报道了首例五元环内 金属卡拜化合物——金属杂戊搭炔。该五元环内金属卡拜存在着极大的环张力， 具有更高的反应活性。本论文研究了金属杂戊搭炔的五元环内金属卡拜键与各类 亲电亲核试剂的反应，并发展了以金属杂戊搭炔为起始原料构筑新型金属杂稠环 的方法。主要内容概括如下： 第一章为绪论，结合本论文的研究内容，简述了金属卡拜反应性质，并对金 属杂稠环化学进行了概述。此外，对金属杂稠环化合物的物理性能以及潜在应用 也进行了简要介绍。 第二章主要研究了锇杂戊搭炔和多种亲电...Metal carbenes and carbynes are organometallic compounds containing metal-carbon multiple bonds, which play an important role in organic synthesis owing to their unique structures and reactivities. Recently, our group reported the first five-membered cyclic metal carbyne complexes, metallapentalynes, which are more reactive because of the large ring strain. In this dissertation, we studied the...学位：理学博士院系专业：化学化工学院_有机化学学号：2052013015383

Reaction Chemistry of Ruthenapentalyne

金属杂戊搭炔是一类特殊的金属桥位型金属杂稠芳环。一方面，与类似的有机反芳香性戊搭烯/炔分子相比，其桥位金属可导致芳香性并稳定双环体系；另一方面，极度弯曲的环内卡拜键表现出丰富的反应性质。锇杂戊搭炔作为首例被报道的金属杂戊搭炔，其反应性已被系统研究，并由此衍生出一系列结构多样的锇杂戊搭烯分子。这些化合物一方面丰富了金属杂稠环芳香家族；另一方面，独特结构引发了独特的性能，有望应用于材料、能源及生命科学等领域。钌杂戊搭炔作为金属杂戊搭炔化学的新成员，其相关反应性研究很少，钌杂戊搭烯的种类也相对较少。本论文致力于研究钌杂戊搭炔的反应性，系统研究了钌杂戊搭炔与亲电试剂、亲核试剂的反应，构筑了一系列结构新...As a distinct member of metal-bridged fused metallaaromatics, metallapentalynes are very attractive for both experimental chemists and theoretical chemists. The introduction of bridge-head metal leads to the aromaticity and stabilizes the bicyclic rings, compared to the antiaromatic organic countpart. In addition, metallapentalynes exhibit unique reactivity due to the extremely high ring strain of...学位：理学硕士院系专业：化学化工学院_有机化学学号：2052014115154

Pyridyl disulfide reaction chemistry : an efficient strategy toward redox-responsive cyclic peptide–polymer conjugates

Cyclic peptide–polymer conjugates are capable of self-assembling into supramolecular polymeric nanotubes driven by the strong multiple hydrogen bonding interactions between the cyclic peptides. In this study, we have engineered responsive nanotubes by introducing a cleavable bond that responds to a reductant utilizing pyridyl disulfide reaction chemistry. Reactions between a cysteine containing cyclic peptide (CP-SH) and pyridyl disulfide containing polymers were initially studied, leading to the quantitative formation of cyclic peptide–polymer conjugates. An asymmetric cyclic peptide–polymer conjugate (PEG-CP-S-S-pPEGA) was then synthesized via orthogonal pyridyl disulfide reaction chemistry and NHS coupling chemistry. The disulfide linker formed by the pyridyl disulfide reaction chemistry was then selectively reduced to thiols in the presence of a reductant, enabling the transition of the conjugates from nonassembling unimers to self-assembled supramolecular polymeric nanotubes. It is anticipated that the pyridyl disulfide reaction chemistry will not only enrich the methodology toward the synthesis of cyclic peptide–polymer conjugates, but also lead to the construction of a new family of redox-responsive cyclic peptide–polymer conjugates and supramolecular polymeric nanotubes with tailored structures and functionalities

Silicon material task. Part 3: Low-cost silicon solar array project

The feasibility of a process for carbon reduction of low impurity silica in a plasma heat source was investigated to produce low-cost solar-grade silicon. Theoretical aspects of the reaction chemistry were studied with the aid of a computer program using iterative free energy minimization. These calculations indicate a threshold temperature exists at 2400 K below which no silicon is formed. The computer simulation technique of molecular dynamics was used to study the quenching of product species

Reaction Chemistry of Silver(I) Trifluoromethanesulfonate Complexes of Nitrogen-Confused \u3cem\u3eC\u3c/em\u3e-Scorpionates

Two new C-scorpionate ligands with a bis(3,5-dimethylpyrazol-1-yl)methyl group bound to the 3 position of either an N-tosyl (TsL*) or an N–H pyrazole (HL*) ring have been prepared. The silver(I) complexes of these new ligands and the two previously reported analogous ligands with unsubstituted bis(pyrazol-1-yl)methyl groups (TsL and HL) in both 1:1 and 2:1 ligand/metal ratios were investigated to explore the effects of ligand sterics on their physical and chemical properties. The structurally characterized derivatives of the type [Ag(L)2](OTf) are four-coordinate, where the confused pyrazolyl is not bound to the metal. On the other hand, three 1:1 complexes [Ag(L)](OTf) had all pyrazolyls bound, while the μ–κ1,κ1-TsL derivative had an unbound confused pyrazolyl. The molecularity of the latter four ranged from polymeric to dimeric to monomeric in the solid with increasing steric bulk of the ligand. The utility of these complexes in stoichiometric ligand-transfer reactions and in styrene aziridination was demonstrated. Thus, tricarbonylmanganese(I) complexes were prepared as kinetically inert models for comparative solution diffusion NMR studies. Also, [Fe(HL)2](OTf)2 was prepared for similar reasons and to compare the effects of anion on spin-crossover properties

Coupled Motions Direct Electrons along Human Microsomal P450 Chains

Directional electron transfer through biological redox chains can be achieved by coupling reaction chemistry to conformational changes in individual redox enzymes

On the formation of glycolaldehyde in dense molecular cores

Glycolaldehyde is a simple monosaccharide sugar linked to prebiotic chemistry. Recently, it was detected in a molecular core in the star-forming region G31.41+0.31 at a reasonably high abundance. We investigate the formation of glycolaldehyde at 10 K to determine whether it can form efficiently under typical dense core conditions. Using an astrochemical model, we test five different reaction mechanisms that have been proposed in the astrophysical literature, finding that a gas-phase formation route is unlikely. Of the grain-surface formation routes, only two are efficient enough at very low temperatures to produce sufficient glycolaldehyde to match the observational estimates, with the mechanism culminating in CH3OH + HCO being favored. However, when we consider the feasibility of these mechanisms from a reaction chemistry perspective, the second grain-surface route looks more promising, H3CO + HCO

Molecular Identifications in Experiments with Astronomical Ice Analogues: New Data, Old Strategies, and the N2 + Acetone System

A recent publication on the radiation chemistry and IR spectroscopy of N2 plus acetone ices is used to illustrate some of the difficulties encountered in the study of astronomical ice analogues. Concerns and problems are identified and suggestions for their solution are presented, including new infrared (IR) spectra of amorphous ices. The hazards of using peak positions alone for assignments of the IR spectra of irradiated ices are illustrated, and the importance of considering the underlying reaction chemistry is shown. Several experiments are proposed as a way to investigate the behaviour of acetone in cold, extraterrestrial environments. Electronic versions of IR spectra are provided and several new refractive indices of ices are reported

Reaction Chemistry Of Epoxides With Fluorinated Carboxylic Acids

During measurements designed to develop a chiral tag rotational spectroscopy methodology for establishing the absolute configuration of a known persistent fluorinated carboxylic acid pollutant (FRD-903), an interesting reaction chemistry was observed. In several cases, highly fluorinated carboxylic acids participate in ring opening of epoxides under ambient conditions. Reactions of three fluorinated carboxylic acids, difluoroacetic acid, trifluoroacetic acid, and pentafluoropropionic acid, with propylene oxide (PO) were explored. The reactions were performed externally to the spectrometer and internally in the gas phase by flowing PO over the fluorinated acid samples. Reactions were performed by adding 4:1 molar equivalents of PO to carboxylic acid, and each reaction was highly exothermic. The reaction mixtures were analyzed by rotational spectroscopy using a chirped-pulsed Fourier transform rotational spectrometer. These measurements showed that the reaction products are created through epoxide ring-opening at both epoxide ring carbons. This reaction chemistry, in principle, offers a way to perform chiral analysis through covalent tagging, but this application would require retention of configuration in the reaction. The reaction products were subsequently chiral tagged to determine the extent of configuration retention. These experiments show that the products, both the ring-opening at the least- and most-substituted carbon on the epoxide ring, are racemized. While these results are not useful for obtaining the absolute configuration, these results further our understanding of the chemistry involved in these reactions. Covalently modifying fluorinated carboxylic acids can be achieved, and establishing absolute configuration could be possible with a more controlled reaction to prevent racemization of the chiral center on the epoxide