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

氰酸盐的未知重同源物（PnCO−,Pn = Sb, Bi）将被合成，辉锑矿和铋矿衍生物的羧化反应是主要策略。目的是合成这些试剂在多克尺度，使他们的化学探索。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，这是该项目的第二部分。与其他假卤化物的相似之处和差异将得到解决。通过复分解反应，所讨论的假卤化物的游离酸将被合成。由13-15族轻元素的假卤化物衍生的小分子化合物也将被研究。控制PnCO -的（电）化学氧化应该产生（间）假卤素。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的氨基酸构建块Pn -，随后从溶液中靶向构建锌离子。综合新的结构主题是这个跨学科子项目的目的。所有化合物都将在结构和性质方面进行彻底的表征，包括晶体结构解析、振动和核磁共振光谱研究、磁性测量和固体和分子方法的量子力学计算。

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.