铁基博酸盐:合成,结构特征和用于制备铁基聚合物的应用
Matthias Scheibitz1, Haiyan Li, Jan Schnorr
1Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany.
Journal of the American Chemical Society
|October 20, 2009
概括
合成和表征了新的铁基聚合物. 这些新型材料具有独特的特性,包括与较小分子相比,红移紫外线吸收,这表明在材料科学中的潜在应用.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物化学 聚合物化学
- 材料科学 材料科学 材料科学
背景情况:
- 铁衍生物是有机金属化学中的多功能构建模块.
- 化合物具有独特的反应性和结构多样性.
- 开发具有定制电子性能的新型聚合物材料具有显著的兴趣.
研究的目的:
- 合成和描述新型单基和双基铁基酸盐.
- 研究这些酸盐及其相应酸盐的反应性.
- 开发新的铁基聚合物并研究它们的特性.
主要方法:
- 使用铁基和化的前体合成铁基化酸盐.
- 用于聚合物的结构性确定的X射线晶体学.
- 酸盐与三甲基化的反应产生酸盐.
- 使用NMR,IR,UV-vis和MALDI-TOF质谱法对铁乙烯聚合物的聚合和表征.
主要成果:
- 成功合成单基和双基铁基酸盐,形成二基和四基聚合物.
- 生产铁基和它们随后的凝结以形成铁基聚合物.
- 合成含有与结合的乙烯基组的新型铁基聚合物,呈现红移紫外线吸收.
结论:
- 这项研究表明,新型铁基聚合物获得的途径很简单.
- 合成的聚合物由于其扩展的结合,具有独特的电子特性.
- 这些发现为开发新的功能性有机金属聚合物开辟了道路.
相关概念视频
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Preparation of Alcohols via Addition Reactions
Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...


