title: Oxidation of a P-C Bond under Mild Conditions.
abstract: The reactivity of phosphenium dication [(Ph3P)2C-P-NiPr2](2+), 1(2+), towards pyridine N-oxide (O-py) has been investigated. The resulting oxophosphonium dication [(Ph3P)2C(NiPr2)P(O)(O-py)](2+), 2(2+), was surprisingly stabilized by a less nucleophilic O-py ligand instead of pyridine (py). This compound was then identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P-C bond through a mechanism usually observed for Baeyer-Villiger oxidations. This oxygen insertion appears to be the first example of a Baeyer-Villiger oxidation involving O-py.
authors.affiliation: SPMS-Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, (Singapore), Fax: (+65) 6791-1961.
authors.forename: Gordana
authors.initials: G
authors.lastname: Ilić
authors.affiliation: SPMS-Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, (Singapore), Fax: (+65) 6791-1961.
authors.forename: Rakesh
authors.initials: R
authors.lastname: Gaguly
authors.affiliation: Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12-16, 11000 Belgrade (Republic of Serbia). milena@ffh.bg.ac.rs.
authors.forename: Milena
authors.initials: M
authors.lastname: Petković
authors.affiliation: SPMS-Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, (Singapore), Fax: (+65) 6791-1961. dvidovic@ntu.edu.sg.
authors.forename: Dragoslav
authors.initials: D
authors.lastname: Vidović
keywords: Baeyer-Villiger oxidation; Criegee intermediate; PC bond oxidation; main-group chemistry; phosphenium dication