Conversion of haloform to carbonate by iridium N-heterocyclic carbene complexes and silver(i) oxide

Abstract

The reaction between haloform, the complexes [Cp*IrCl2(κC-MeNC3H2NCH2Ar)] (Ar = C6H3F2-2,6, C6H3F-2-Cl-6, C6H3Me2-2,6) and silver(i) oxide proceeded by carbon–halogen bond fission to yield the carbonate complexes [Cp*Ir(κ2O-CO3)(κC-MeNC3H2NCH2Ar)].

Methanol-Mediated Formation of an Iridium(III) NHC/Azolato Chelate Complex: An Experimental and Theoretical Study

“…Because the reaction was performed under purified argon, the presence of the carbonato ligand cannot result from impurities. It is instead caused by the known oxidation of dichloromethane in the presence of silver oxide . The preparation of several additional iridium­(III) carbonato complexes has been reported. − …”

“…It is instead caused by the known oxidation of dichloromethane in the presence of silver oxide . The preparation of several additional iridium­(III) carbonato complexes has been reported. − …”

“…It is instead caused by the known oxidation of dichloromethane in the presence of silver oxide. 46 The preparation of several additional iridium(III) carbonato complexes has been reported. 46−48 Complex [1] was fully characterized by NMR spectroscopy and by an X-ray diffraction (XRD) analysis (see the Supporting Information).…”

(η5-Pentamethylcyclopentadienyl)iridium{1,3-bis(2,3,4,5,6-pentafluorobenzyl)imidazolin-2-ylidene}dichloride

“…Group 9 metal complexes of N-heterocycle carbene (NHC) ligands bearing polyfluoroaryl substituents have provided a fertile area of research recently. Importantly, these complexes possess catalytic properties [1,2], including for base-free dynamic resolution in combination with an enzyme [3], and display unusual reactivity [4][5][6][7], including carbonfluorine bond activation [8,9]. The structures of some of the complexes have been determined in single-crystal X-ray diffraction studies [5][6][7][8][9][10][11][12][13], but of these, most complexes contain a monofluorinated substituent, and only four bear a perfluorinated aryl substituent.…”

“…Importantly, these complexes possess catalytic properties [1,2], including for base-free dynamic resolution in combination with an enzyme [3], and display unusual reactivity [4][5][6][7], including carbonfluorine bond activation [8,9]. The structures of some of the complexes have been determined in single-crystal X-ray diffraction studies [5][6][7][8][9][10][11][12][13], but of these, most complexes contain a monofluorinated substituent, and only four bear a perfluorinated aryl substituent. The crystal structure of the dichloromethane solvate of the complex Cp*IrCl 2 {κC-C 6 H 5 CH 2 NC 3 H 2 NCH 2 C 6 F 5 } (1) (Figure 1) [13] display a number of short intermolecular distances that suggest significant attractive interactions: π-π stacking between the phenyl ring of molecule of 1 and the pentafluorophenyl ring of another, hydrogen bonding between the hydrogen atoms of the imidazolin-2-ylidene ring of one molecule of 1 and the chloride ligands of another, hydrogen bonding between the hydrogen atoms of a dichloromethane molecule and the chloride ligands, and an interaction between one of the chlorine atoms of dichloromethane and the C 5 ring of the pentamthylcyclopentadienyl ligand of 1.…”