Ho Luong Phong, Neitzel Angelika, Bannenberg Thomas, Tamm Matthias
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.
Chemistry. 2022 Jan 19;28(4):e202104139. doi: 10.1002/chem.202104139. Epub 2021 Dec 22.
The lithium salts of anionic N-heterocyclic thiones and selones [{(WCA-IDipp)E}Li(toluene)] (1: E=S; 2: E=Se; WCA=B(C F ) , 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 SiCl, to furnish the silylated adducts (WCA-IDipp)ESiMe (3: E=S; 4: E=Se). The reaction of the latter with [(η -C Me )MCl ] (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half-sandwich complexes [{(WCA-IDipp)E}MCl(η -C Me )] (5-8). The direct reaction of the lithium salts 1 and 2 with a half or a full equivalent of [M(COD)Cl] (M=Rh, Ir) afforded the monometallic complexes [{(WCA-IDipp)E}M(COD)] (9-12) or the bimetallic complexes [μ -{(WCA-IDipp)E}M (COD) (μ -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.
含咪唑骨架中弱配位阴离子（WCA）硼酸酯部分的阴离子型N-杂环硫酮和硒酮的锂盐[{(WCA-IDipp)E}Li(甲苯)]（1：E = S；2：E = Se；WCA = B(C₆F₅)₄，IDipp = 1,3-双(2,6-二异丙基苯基)咪唑啉-2-亚基）与Me₃SiCl反应，得到硅烷化加合物(WCA-IDipp)ESiMe₃（3：E = S；4：E = Se）。后者与[(η⁵-C₅Me₅)MCl₂]（M = Rh，Ir）反应，得到铑(III)和铱(III)半夹心配合物[{(WCA-IDipp)E}MCl(η⁵-C₅Me₅)]（5 - 8）。锂盐1和2与半当量或全当量的[M(COD)Cl]（M = Rh，Ir）直接反应，分别得到单金属配合物[{(WCA-IDipp)E}M(COD)]（9 - 12）或双金属配合物[μ-{(WCA-IDipp)E}M₂(COD)₂(μ-Cl)]（13 - 16）。通过密度泛函理论（DFT）计算研究了这些配合物中的键合情况，结果表明硫醇盐或硒醇盐配体具有可忽略不计的金属-硫属元素π相互作用。
