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Reactivity of 2-phospa- und 2-arsaethynolate and Synthesis of their heavier homologues 2-stiba- and 2-bismuthinaethynolate

2-phospa- 和 2-arsaethenolate 的反应性及其较重同系物 2-stiba- 和 2-bismuthinaethynolate 的合成

基本信息

批准号：
388040773
负责人：
Dr. Frank Tambornino
金额：
--
依托单位：
Chemistry Research Laboratory
依托单位国家：
德国
项目类别：
Research Fellowships
财政年份：
2017
资助国家：
德国
起止时间：
2016-12-31 至 2018-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/388040773?language=en
关键词：
Reactivity phospa und arsaethynolate Synthesis

项目摘要

The unknown heavy homologues of cyanate (PnCO−, Pn = Sb, Bi) are to be synthesized, carboxylation reactions of stibine- and bismuthine derivates are central strategies. The aim is the synthesis of those reagents in multi-gram scales to enable exploration of their chemistry. The coordination and molecule chemistry of PnCO− type anions (Pn = P, As, Sb, Bi) is largely unknown and constitutes the second part of this project. Parallels and differences towards other pseudohalogenides will be worked out. By means of metathesis reactions, the free acids of the pseudohalogenides in question will be synthesized. Small molecular compounds deriving from the pseudohalogenides with light elements of group 13–15 will also be investigated. Controlled (electro)chemical oxidation of PnCO− is supposed to yield (inter)pseudohalogenes. Coordination of d- and f-elements will be investigated for PnCO− (Pn = As, Sb, Bi). Photo- and thermochemical decarboxylation lead to formation of monoanionic pnictide building blocks Pn− and subsequently to targeted construction of Zintl-ions from solution. Synthesis of new structural motifs are the aim of this interdisciplinary sub-project. All compounds will be characterized thoroughly with respect to structure and properties, including cystallographic structure elucidation, vibrational and NMR spectroscopical investigations, magnetic measurements and quantum mechanical calculations with solid-state and molecule methods.

氰酸盐的未知重同系物（PnCO−，Pn = Sb，Bi）将被合成，锑化氢和铋化氢衍生物的羧化反应是核心策略。目标是在多克规模上合成这些试剂，以探索它们的化学性质。PnCO−型阴离子（Pn = P，As，Sb，Bi）的配位和分子化学在很大程度上是未知的，构成了该项目的第二部分。将找出与其他拟卤化物的相似之处和差异。通过复分解反应，将合成所讨论的拟卤化物的游离酸。小分子化合物衍生的拟卤化物与轻元素的第13-15族也将进行研究。PnCO−的受控（电）化学氧化被认为会产生（间）拟卤素。将研究PnCO−（Pn = As，Sb，Bi）中d-和f-元素的配位。光化学和热化学脱羧导致形成单阴离子磷属元素化物结构单元Pn−，随后从溶液中定向构建锌离子。新结构基序的合成是这个跨学科子项目的目标。所有化合物的结构和性质将进行彻底的表征，包括晶体结构解析，振动和NMR光谱研究，磁性测量和量子力学计算与固态和分子方法。