eprintid: 27586
rev_number: 30
userid: 1418
dir: disk0/00/02/75/86
datestamp: 2016-04-06 15:36:06
lastmod: 2021-06-12 22:56:30
status_changed: 2016-04-06 15:36:06
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Pan, X
creators_name: Vallet, AL
creators_name: Schweizer, S
creators_name: Dahbi, K
creators_name: Delpech, B
creators_name: Blanchard, N
creators_name: Graff, B
creators_name: Geib, SJ
creators_name: Curran, DP
creators_name: Lalevée, J
creators_name: Lacoîte, E
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creators_email: geib@pitt.edu
creators_email: curran@pitt.edu
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creators_id: GEIB
creators_id: CURRAN
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creators_orcid: 0000-0002-9160-7857
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title: Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
abstract: Reactions of 1,3-dimethylimidazol-2-ylidene-borane (diMe-Imd-BH 3) and related NHC-boranes with diaryl and diheteroaryl disulfides provide diverse NHC-boryl monosulfides (diMe-Imd-BH2SAr) and NHC-boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC-borane in the primary NHC-boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC-boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible. © 2013 American Chemical Society.
date: 2013-07-17
date_type: published
publication: Journal of the American Chemical Society
volume: 135
number: 28
pagerange: 10484 - 10491
refereed: TRUE
issn: 0002-7863
id_number: 10.1021/ja403627k
pmid: 23718209
mesh_headings: Boranes--chemistry
mesh_headings: Disulfides--chemistry
mesh_headings: Free Radicals--chemical synthesis
mesh_headings: Free Radicals--chemistry
mesh_headings: Heterocyclic Compounds--chemical synthesis
mesh_headings: Heterocyclic Compounds--chemistry
mesh_headings: Methane--analogs & derivatives
mesh_headings: Methane--chemical synthesis
mesh_headings: Methane--chemistry
mesh_headings: Molecular Structure
chemical_names: Boranes
chemical_names: Disulfides
chemical_names: Free Radicals
chemical_names: Heterocyclic Compounds
chemical_names: carbene
chemical_names: Methane
citation:   Pan, X and Vallet, AL and Schweizer, S and Dahbi, K and Delpech, B and Blanchard, N and Graff, B and Geib, SJ and Curran, DP and Lalevée, J and Lacoîte, E  (2013) Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides.  Journal of the American Chemical Society, 135 (28).  10484 - 10491.  ISSN 0002-7863     
document_url: http://d-scholarship-dev.library.pitt.edu/27586/1/licence.txt