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Yellow Arsenic as starting Material– Differences and Similarities in Its Reactivity to White Phosphorus

Subject Area Inorganic Molecular Chemistry - Synthesis and Characterisation
Term from 2020 to 2024
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 440970708
 
Final Report Year 2024

Final Report Abstract

The aim of the project was the systematic investigation of the reactivity of yellow arsenic towards main group element compounds or special complexes of transition metals in order to draw comparisons with corresponding reactions of white phosphorus. The particular difficulties in arsenic chemistry lie in the As NMR spectroscopy, which, as opposed to the P NMR spectroscopy, cannot be applied due to the high quadrupole moment (I = 3/2) and the resulting large line width, where only highly symmetrical arsenic compounds can be detected. The poor solubility of As4 at low temperatures in any solvent also impairs the detection of first kinetically stable reaction products. It is therefore necessary to obtain single crystals for X- ray structure analysis in order to gain insight into the reaction progress. Nevertheless, systematic investigations of the reactivity of As4 towards CAAAs, linked disilylenes or Al(I) and Ga(I) nacnac compounds were successfully carried out in the field of main group element chemistry, showing that As products, analogous to the P4 chemistry but unprecedented for As, are formed with slight structural differences depending on the substituent pattern especially at the CAACs. Thus, the number of main group element-based arsenic compounds could be significantly expanded. The first mixed P/As compounds of the main group elements were also obtained by using AsP3. Due to the low As-As binding energy as compared to the Pn chemistry, As-rich derivatives could only sporadically be isolated so that As-poorer derivatives represent the thermodynamic products of the reactions. In the reaction of As 4 with selected metal complexes of the electron-rich transition metals, as a rule, new Asn complexes analogous to the chemistry of P4 were isolated, despite of clear differences depending on the ligand pattern at the transition metal. By using special bimetallic complexes of copper, novel binding modes of intact P4 or As4 tetrahedra could be identified so that the structural diversity of the various As4-bound complexes surpasses that of the P4 binding modes and testifies to the higher flexibility in the coordination form of the As4 tetrahedron.

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