Cationic Iridium(I) NHC‐Phosphinidene Complexes and Their Application in Hydrogen Isotope Exchange Reactions. Issue 16 (9th May 2022)

• Record Type: Journal Article
• Authors: Peters, Marius; Bockfeld, Dirk; Tamm, Matthias
• Is Part Of: European journal of inorganic chemistry. Volume 2022:Issue 16(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-09
• Subjects: Carbene ligands -- Homogeneous catalysis -- Hydrogen isotope exchange -- Iridium -- Phosphinidene ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202200148
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The reaction of the dimeric iridium complex [Ir(cod)Cl]2 (cod=1, 5‐cyclooctadiene) with the N‐heterocyclic carbene‐phosphinidene adduct (IDipp)PH (1, IDipp=1, 3‐bis(2, 6‐diisopropylphenyl)imidazolin‐2‐ylidene) afforded the neutral bimetallic iridium(I) complex [μ‐{(IDipp)PH}{Ir(cod)Cl}2 ] (2 ), and further addition of IDipp(PH) (1 ) yielded the corresponding monometallic iridium(I) complex [{(IDipp)PH}Ir(cod)Cl] (3 ). Dechlorination of these complexes with sodium tetrakis[3, 5‐bis(trifluoromethyl)phenyl]borate (NaBAr F 4 ) yielded their cationic derivatives [{μ‐(IDipp)PH}{Ir(cod)}2 {μ‐Cl}][BAr F 4 ] (4 ) and [{(IDipp)PH}Ir(cod)(PPh3 )][BAr F 4 ] (5 ). All complexes were structurally characterized and showed the expected square‐planar coordination geometry and significant polarization of the P−C bond of the NHC‐phosphinidene adduct upon metal coordination. The complexes 4 and 5 were tested for their applicability in catalytic H/D exchange reactions, and both complexes showed high activity for a broad range of aromatic substrates, ranging from ketones, amides, esters, nitro compounds and heterocycles. Abstract : Cationic Ir(I) NHC‐phosphinidene complexes have been tested in H/D exchange reactions with various aromatic substrates. The catalysts show a level of catalytic activity similar to those of reported and established cationic Kerr‐type HIE catalysts.