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Title: Synthesis, Electronic Properties and Reactivity of [B12X11(NO2)]2– (X=F–I) Dianions

Journal Article · · Chemistry - A European Journal
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [1]; ORCiD logo [3]
  1. Univ. of Leipzig (Germany)
  2. Univ. of Wuppertal (Germany)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Univ. of Leipzig (Germany); Leibniz Inst. for Surface Engineering (IOM), Leipzig (Germany)
+ Show Author Affiliations

Nitro-functionalized undecahalogenated closo-dodecaborates [B12X11(NO2)]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 NO2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B12X12]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 [B12X11O]2–.. Theoretical investigations suggest that the loss of NO. proceeds via the rearrangement product [B12X11(ONO)]2–. The O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formation by radical recombination of [B12X11O]2–. and NO. is demonstrated.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1770561
Report Number(s):
PNNL-SA-154957
Journal Information:
Chemistry - A European Journal, Vol. 26, Issue 64; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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