Oxidative addition of halogens to a Cycloneophylplatinum(II) complex and evidence for C–H bond activation at Platinum(IV)

Publication date: Available online 26 January 2020Source: Journal of Organometallic ChemistryAuthor(s): Mahmood Azizpoor Fard, Richard J. PuddephattAbstractThe reactions of halogens or their equivalent with the cycloneophylplatinum (II) complex [Pt (CH2CMe2C6H4) (phen*)], phen* = 3,4,7,8-tetramethyl-1,10-phenanthroline, are reported. The reactions occur by kinetically controlled trans oxidative addition to form trans-[PtX2(CH2CMe2C6H4) (phen*)], X = Cl, Br, I, and, when X = Br or I, these equilibrate slowly with the products of cis oxidative addition cis-[PtX2(CH2CMe2C6H4) (phen*)], X = Br, I. The complex cis-[PtCl2(CH2CMe2C6H4) (phen*)] was prepared by reaction of [PtCl(CH2CMe2C6H5) (phen*)] with chlorine equivalent, in a reaction that involves a cyclometalation step at platinum (IV). The unusual complex [PtCl(CH2CMe2C6H4) (CH2CMe2C6H5) (phen*)], which contains both a neophyl and a cycloneophyl group, was isolated as a minor product from reaction of [Pt (CH2CMe2C6H4) (phen*)] with HCl. The mechanisms of several of these reactions are elucidated and seven structure determinations are reported.Graphical abstract

Source: Journal of Organometallic Chemistry - January 27, 2020 Category: Chemistry Source Type: research