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Rhodium and Iridium Complexes of Anionic Thione and Selone Ligands Derived from Anionic N-Heterocyclic Carbenes.

ABSTRACT: The lithium salts of anionic N-heterocyclic thiones and selones [{(WCA-IDipp)E}Li(toluene)] (1: E=S; 2: E=Se; WCA=B(C₆ F₅ )₃ , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene), which contain a weakly coordinating anionic (WCA) borate moiety in the imidazole backbone were reacted with Me₃ SiCl, to furnish the silylated adducts (WCA-IDipp)ESiMe₃ (3: E=S; 4: E=Se). The reaction of the latter with [(η⁵ -C₅ Me₅ )MCl₂ ]₂ (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half-sandwich complexes [{(WCA-IDipp)E}MCl(η⁵ -C₅ Me₅ )] (5-8). The direct reaction of the lithium salts 1 and 2 with a half or a full equivalent of [M(COD)Cl]₂ (M=Rh, Ir) afforded the monometallic complexes [{(WCA-IDipp)E}M(COD)] (9-12) or the bimetallic complexes [μ₂ -{(WCA-IDipp)E}M₂ (COD)₂ (μ₂ -Cl)] (13-16), respectively. The bonding situation in these complexes has been investigated by means of density functional theory (DFT) calculations, revealing thiolate or selenolate ligand character with negligible metal-chalcogen π-interaction.

SUBMITTER: Ho LP

PROVIDER: S-EPMC9305287 | biostudies-literature |

REPOSITORIES: biostudies-literature

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