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Rhodium and Iridium Complexes of Anionic Thione and Selone Ligands Derived from Anionic N‐Heterocyclic Carbenes
Author(s) -
Ho Luong Phong,
Neitzel Angelika,
Bannenberg Thomas,
Tamm Matthias
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202104139
Subject(s) - chemistry , iridium , rhodium , moiety , medicinal chemistry , adduct , bimetallic strip , imidazole , ligand (biochemistry) , lithium (medication) , chalcogen , polymer chemistry , toluene , stereochemistry , organic chemistry , metal , catalysis , medicine , biochemistry , receptor , endocrinology
The lithium salts of anionic N‐heterocyclic thiones and selones [{(WCA‐IDipp)E}Li(toluene)] ( 1 : E=S; 2 : E=Se; WCA=B(C 6 F 5 ) 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 Me 3 SiCl, to furnish the silylated adducts (WCA‐IDipp)ESiMe 3 ( 3 : E=S; 4 : E=Se). The reaction of the latter with [( η 5 ‐C 5 Me 5 )MCl 2 ] 2 (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half‐sandwich complexes [{(WCA‐IDipp)E}MCl( η 5 ‐C 5 Me 5 )] ( 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 [ μ 2 ‐{(WCA‐IDipp)E}M 2 (COD) 2 ( μ 2 ‐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.