PMID- 36097953
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20220921
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 24
IP  - 36
DP  - 2022 Sep 21
TI  - Binding of saturated and unsaturated C(6)-hydrocarbons to the electrophilic anion 
      [B(12)Br(11)](-): a systematic mechanistic study.
PG  - 21759-21772
LID - 10.1039/d2cp01042a [doi]
AB  - The highly reactive gaseous ion [B(12)Br(11)](-) is a metal-free closed-shell 
      anion which spontaneously forms covalent bonds with hydrocarbon molecules, 
      including alkanes. Herein, we systematically investigate the reaction mechanism 
      for binding of [B(12)Br(11)](-) to the five hexane isomers yielding 
      [B(12)Br(11)(C(6)H(14))](-), as well as to cyclohexane and several hexene isomers 
      (yielding [B(12)Br(11)(C(6)H(12))](-)) using collision-induced dissociation 
      (CID), infrared photodissociation spectroscopy (IRPD) and computational methods. 
      CID of the different [B(12)Br(11)(C(6)H(14))](-) ions results in distinct 
      fragmentation patterns dependent on the structure of the hexane isomer. The 
      observed fragmentation reactions provide insights into the addition mechanism of 
      [B(12)Br(11)](-) to hexane. Based on the observed CID patterns, we identified 
      that either B-C bond formation through heterolytic C-C or C-H bond cleavages or 
      B-H bond formation through heterolytic C-H cleavage occur dependent on the 
      structure of the hexane isomer. Meanwhile, we observe identical CID spectra of 
      adducts originating from isomers of C(6)H(12). Spectroscopic investigations of 
      adducts of 1-hexene and cyclohexane indicate the same product structure with an 
      open C(6) chain. Computational investigations evidenced that low lying transition 
      states are present, which enable a ring opening reaction of cyclohexane when 
      binding to [B(12)Br(11)](-).
FAU - Ma, Xin
AU  - Ma X
AUID- ORCID: 0000-0002-7058-0165
AD  - Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 
      47907, USA.
AD  - School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 
      Atlantic Drive NW, Atlanta, GA, 30332, USA.
FAU - Rohdenburg, Markus
AU  - Rohdenburg M
AUID- ORCID: 0000-0001-8533-3610
AD  - Wilhelm-Ostwald-Institut fur Physikalische und Theoretische Chemie, Universitat 
      Leipzig, 04103, Leipzig, Germany.
FAU - Knorke, Harald
AU  - Knorke H
AUID- ORCID: 0000-0001-6070-1827
AD  - Wilhelm-Ostwald-Institut fur Physikalische und Theoretische Chemie, Universitat 
      Leipzig, 04103, Leipzig, Germany.
FAU - Kawa, Sebastian
AU  - Kawa S
AUID- ORCID: 0000-0002-4624-1630
AD  - Wilhelm-Ostwald-Institut fur Physikalische und Theoretische Chemie, Universitat 
      Leipzig, 04103, Leipzig, Germany.
FAU - Liu, Judy Kuan-Yu
AU  - Liu JK
AD  - Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 
      47907, USA.
FAU - Apra, Edoardo
AU  - Apra E
AUID- ORCID: 0000-0001-5955-0734
AD  - Environmental Molecular Sciences Laboratory, Pacific Northwest National 
      Laboratory, Richland, WA, 99352, USA.
FAU - Asmis, Knut R
AU  - Asmis KR
AUID- ORCID: 0000-0001-6297-5856
AD  - Wilhelm-Ostwald-Institut fur Physikalische und Theoretische Chemie, Universitat 
      Leipzig, 04103, Leipzig, Germany.
FAU - Azov, Vladimir A
AU  - Azov VA
AUID- ORCID: 0000-0002-2340-2198
AD  - Department of Chemistry, University of the Free State, PO Box 339, 9300 
      Bloemfontein, South Africa.
FAU - Laskin, Julia
AU  - Laskin J
AUID- ORCID: 0000-0002-4533-9644
AD  - Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 
      47907, USA.
FAU - Jenne, Carsten
AU  - Jenne C
AUID- ORCID: 0000-0002-5913-3989
AD  - Anorganische Chemie, Fakultat fur Mathematik und Naturwissenschaften, Bergische 
      Universitat Wuppertal, 42119, Wuppertal, Germany.
FAU - Kenttamaa, Hilkka I
AU  - Kenttamaa HI
AUID- ORCID: 0000-0001-8988-6984
AD  - Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 
      47907, USA.
FAU - Warneke, Jonas
AU  - Warneke J
AUID- ORCID: 0000-0002-3233-7412
AD  - Wilhelm-Ostwald-Institut fur Physikalische und Theoretische Chemie, Universitat 
      Leipzig, 04103, Leipzig, Germany.
AD  - Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, D-04318, 
      Leipzig, Germany. jonas.warneke@uni-leipzig.de.
LA  - eng
PT  - Journal Article
DEP - 20220921
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
SB  - IM
EDAT- 2022/09/14 06:00
MHDA- 2022/09/14 06:01
CRDT- 2022/09/13 04:32
PHST- 2022/09/14 06:00 [pubmed]
PHST- 2022/09/14 06:01 [medline]
PHST- 2022/09/13 04:32 [entrez]
AID - 10.1039/d2cp01042a [doi]
PST - epublish
SO  - Phys Chem Chem Phys. 2022 Sep 21;24(36):21759-21772. doi: 10.1039/d2cp01042a.