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

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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.