title: Structure of olefin-imidacloprid and gas-phase fragmentation chemistry of its protonated form.
abstract: One of the major insect metabolites of the widely used neonicotinoid insecticide imidacloprid, 1 (1-[(6-chloro-3-pyridinyl)methyl]-N-nitro-1H-imidazol-2-amine), is the olefin 2. To better understand how the structure of olefin 2 relates to the gas-phase fragmentation of its protonated form, 2H(+), X-ray crystallography, tandem mass spectrometry experiments and DFT calculations were carried out. Olefin 2 was found to be in a tautomeric form where the proton is on the N(1) position of the imidazole ring and forms a hydrogen bond to one of the oxygen atoms of the coplanar nitroamine group. Under conditions of low-energy collision-induced dissociation (CID) in a linear ion trap, 2H(+), formed via electrospray ionization (ESI), fragments via a major loss of water, together with minor competing losses of HNO2 and NO2•.This contrasts with 1H+, which mainly undergoes bond homolysis via NO2• loss. Thus, installation of the double bond in 2 plays a key role in facilitating the loss of water. DFT calculations, carried out using the B3LYP/6-311G++(d,p) level of theory, revealed that loss of water was energetically more favourable compared to HNO2 and NO2• loss. Three multistep, energetically accessible mechanisms were identified for loss of water from 2H(+), and these have the following barriers: (I) direct proton transfer from N(5) of the pyridine to O(1) on the NO2 group (119 kJ mol(-1)); (II) rotation of the N(2)-N(4) bond (117 kJ mol(-1)); (III) 1,3-intramolecular proton transfer between the two oxygen atoms of the NO2 group (145 kJ mol(-1)). Given that the lowest barrier for the losses of HNO2 and NO2• is 156 kJ mol(-1), it is likely that all three water loss mechanisms occur concurrently.
authors.affiliation: School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Roberto
authors.initials: R
authors.lastname: Fusetto
authors.affiliation: School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: White
authors.affiliation: School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Hutton
authors.affiliation: School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Richard A J
authors.initials: RA
authors.lastname: O'Hair
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D000073943:Neonicotinoids; D009574:Nitro Compounds / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D053719:Tandem Mass Spectrometry
chemical_list: D000475:Alkenes; D007093:Imidazoles; D000073943:Neonicotinoids; D009574:Nitro Compounds; D011522:Protons; C082359:imidacloprid