Intramolecular C–H oxidative addition to iridium(i) triggered by trimethyl phosphite in N, N′-diphosphanesilanediamine complexes12. Issue 42 (8th October 2015)

• Record Type: Journal Article
• Authors: Passarelli, Vincenzo; Pérez-Torrente, Jesús J.; Oro, Luis A.
• Is Part Of: Dalton transactions. Volume 44:Issue 42(2015)
• Page Start: 18596
• Page End: 18606
• Publication Date: 2015-10-08
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02886h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The intramolecular C–H oxidative addition in the Ir I (κ 2 P, P ′-SiNP) moiety is triggered by trimethyl phosphite and yields the Ir III H(κ 3 C, P, P ′-{SiNP-H}) scaffold. Abstract : The reaction of [Ir(SiNP)(cod)][PF6 ] ([1 ][PF6 ]) and of IrCl(SiNP)(cod) (5 ) (SiNP = SiMe2 {N(4-C6 H4 CH3 )PPh2 }2 ) with trimethyl phosphite affords the iridium(iii ) derivatives of the formula [IrHCl x (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-C6 H4 CH3 )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 [IrCl x (SiNP){P(OMe)3 }2− x ] (1− x )+ ( x = 0, 4 + ; x = 1, 7 ) should be firstly obtained from2 + and finally should undergo the C–H oxidative addition to iridium(i ) via a concerted intramolecular mechanism. The influence of the counterion of2 + on the outcome of the C–H oxidative addition reaction has also been investigated.