title: Intramolecular C-H oxidative addition to iridium(I) triggered by trimethyl phosphite in N,N'-diphosphanesilanediamine complexes.
abstract: The reaction of [Ir(SiNP)(cod)][PF6] ([1][PF6]) and of IrCl(SiNP)(cod) (5) (SiNP = SiMe2{N(4-C6H4CH3)PPh2}2) with trimethyl phosphite affords the iridium(iii) derivatives of the formula [IrHClx(SiNP-H){P(OMe)3}2-x]((1-x)+) (x = 0, 3(+); x = 1, 6) containing the κ(3)C,P,P'-coordinated SiNP-H ligand (SiNP-H = Si(CH2)(CH3){N(4-C6H4CH3)PPh2}2). The thermally unstable pentacoordinated cation [Ir(SiNP){P(OMe)3}(cod)](+) (2(+)) has been detected as an intermediate of the reaction and has been fully characterised in solution. Also, the mechanism of the C-H oxidative addition has been elucidated by DFT calculations showing that the square planar iridium(i) complexes of the formula [IrClx(SiNP){P(OMe)3}2-x]((1-x)+) (x = 0, 4(+); x = 1, 7) should be firstly obtained from 2(+) and finally should undergo the C-H oxidative addition to iridium(i) via a concerted intramolecular mechanism. The influence of the counterion of 2(+) on the outcome of the C-H oxidative addition reaction has also been investigated.
authors.affiliation: Centro Universitario de la Defensa, Ctra. Huesca s/n, ES-50090 Zaragoza, Spain. passarel@unizar.es.
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Passarelli
authors.forename: Jesús J
authors.initials: JJ
authors.lastname: Pérez-Torrente
authors.forename: Luis A
authors.initials: LA
authors.lastname: Oro
mesh_terms: D002244:Carbon / Q000737:chemistry; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003959:Diamines / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D003959:Diamines; D008024:Ligands; D007495:Iridium; D002244:Carbon; D006859:Hydrogen