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Synthesis, Electronic Properties and Reactivity of [B 12 X 11 (NO 2 )] 2− (X=F–I) Dianions
Author(s) -
Asmis Knut R.,
Beele Björn B.,
Jenne Carsten,
Kawa Sebastian,
Knorke Harald,
Nierstenhöfer Marc C.,
Wang XueBin,
Warneke Jonas,
Warneke Ziyan,
Yuan Qinqin
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003537
Subject(s) - chemistry , raman spectroscopy , x ray photoelectron spectroscopy , cyclic voltammetry , homolysis , substituent , reactivity (psychology) , crystallography , ion , analytical chemistry (journal) , crystal structure , spectroscopy , electrochemistry , radical , stereochemistry , organic chemistry , nuclear magnetic resonance , electrode , medicine , physics , alternative medicine , pathology , optics , quantum mechanics
Nitro‐functionalized undecahalogenated closo ‐dodecaborates [B 12 X 11 (NO 2 )] 2− were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X‐diffraction, mass spectrometry, and gas‐phase ion vibrational spectroscopy. The NO 2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B 12 X 12 ] 2− (X=F–I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum‐chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO . ). The homolytic NO . elimination from the dianion under very soft collisional excitation in gas‐phase ion experiments results in the formation of the radical [B 12 X 11 O] 2−. . Theoretical investigations suggest that the loss of NO . proceeds via the rearrangement product [B 12 X 11 (ONO)] 2− . The O ‐bonded nitrosooxy structure is thermodynamically more stable than the N ‐bonded nitro structure and its formation by radical recombination of [B 12 X 11 O] 2−. and NO . is demonstrated.