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Evidence for the Existence of (SiP 6 H 2 ) 2– and its Homologs as Examples of Binary Nortricyclane‐Type Zintl Anions
Author(s) -
Mitzinger Stefan,
Guggolz Lukas,
Massa Werner,
Dehnen Stefanie
Publication year - 2019
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201800285
Subject(s) - chemistry , crystallography , ternary operation , electrospray ionization , mass spectrometry , protonation , stoichiometry , analytical chemistry (journal) , ion , organic chemistry , chromatography , computer science , programming language
The extraction of stoichiometric ternary K/Si/P, K/Ge/P, and K/Si/As solid mixtures with en/crypt‐222 afforded compounds with binary anions of the respective groups 14/15 elemental combination. Although the analysis of the products turned out to be extremely difficult owing to their intrinsically poor crystallinity and low solubility, we have evidence that one of them contains (SiP 6 H 2 ) 2– anions. Preliminary data from the two other compounds indicate the existence of the heavier Ge/P and Si/As variants as well. The combination of all analytical results, including X‐ray crystallography, energy‐dispersive X‐ray (EDX) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and nuclear magnetic resonance (NMR) spectroscopy, point towards the named composition of the anions and their doubly protonated nature. By this, they represent the first binary Zintl anions of the Si/P and Si/As elemental combination and complement the recent endeavors to synthesize binary Zintl anions of the light(er) p‐block elements. We discuss our attempts to elucidate the clusters' identity and provide our results as the most probable interpretation of the data, additionally corroborated by quantum chemical analyses.