Jump to main content
Jump to site search

Issue 3, 2016
Previous Article Next Article

En route to phosphonato iridium(I) complexes: the decisive effect of an intramolecular hydrogen bond

Author affiliations

Abstract

Pentacoordinated iridium(I) complexes of formula IrCl(SiNP)(tfbb) (1) and IrCl(HNP)2(tfbb) (2) (SiNP = SiMe2{N(4-C6H4CH3)PPh2}2; HNP = NH(4-C6H4CH3)PPh2) have been prepared and fully characterised. Both feature a distorted square pyramidal coordination polyhedron at the metal centre in the solid state and are fluxional in solution. Their reaction with trimethyl phosphite yields the derivatives [Ir(SiNP){P(OMe)3}(tfbb)]Cl ([3]Cl) and Ir{PO(OMe)2}(HNP)2(tfbb) (4). The course of the reaction between IrCl(HNP)2(tfbb) (2) and trimethyl phosphite was elucidated by NMR spectroscopy and DFT calculations, showing that the intermediate [Ir(HNP)2{P(OMe)3}(tfbb)]+ (5+) forms and further reacts with the chloride anion yielding the phosphonato derivative 4 and methyl chloride. The decisive role of the N–H group in the formation of the phosphonato ligand has been established by IR and NMR spectroscopic measurements and by DFT calculations.

Graphical abstract: En route to phosphonato iridium(i) complexes: the decisive effect of an intramolecular hydrogen bond

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Oct 2015, accepted on 18 Nov 2015 and first published on 23 Nov 2015


Article type: Paper
DOI: 10.1039/C5DT04038H
Dalton Trans., 2016,45, 951-962

  •   Request permissions

    En route to phosphonato iridium(I) complexes: the decisive effect of an intramolecular hydrogen bond

    V. Passarelli, J. J. Pérez-Torrente and L. A. Oro, Dalton Trans., 2016, 45, 951
    DOI: 10.1039/C5DT04038H

Search articles by author

Spotlight

Advertisements