Simler Thomas, McCabe Karl N, Maron Laurent, Nocton Grégory
LCM, CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, Route de Saclay Palaiseau 91120 France
LPCNO, UMR 5215, Université de Toulouse-CNRS, INSA, UPS Toulouse France.
Chem Sci. 2022 May 9;13(25):7449-7461. doi: 10.1039/d2sc01798a. eCollection 2022 Jun 29.
The divalent thulium complex [Tm(Cp)] (Cp = 1,2,4-tris(-butyl)cyclopentadienyl) reacts with CO to afford selective CO reductive dimerization and trimerization into ethynediolate (C) and ketenecarboxylate (C) complexes, respectively. DFT calculations were performed to shed light on the elementary steps of CO homologation and support a stepwise chain growth. The attempted decoordination of the ethynediolate fragment by treatment with MeSiI led to dimerization and rearrangement into a 3,4-dihydroxyfuran-2-one complex. Investigation of the reactivity of the C and C complexes towards other electrophiles led to unusual functionalization reactions: while the reaction of the ketenecarboxylate C complex with electrophiles yielded new multicarbon oxygenated complexes, the addition of CO to the ethynediolate C complex resulted in the formation of a very reactive intermediate, allowing C-H activation of aromatic solvents. This original intermolecular reactivity corresponds to an unprecedented functionalization of CO-derived ligands, which is induced by CO.
二价铥配合物[Tm(Cp)]（Cp = 1,2,4-三（叔丁基）环戊二烯基）与CO反应，分别选择性地将CO还原二聚和三聚为乙炔二醇盐（C）和烯酮羧酸盐（C）配合物。进行了密度泛函理论（DFT）计算，以阐明CO同系化的基本步骤并支持逐步的链增长。尝试通过用MeSiI处理使乙炔二醇盐片段脱配位，导致二聚和重排成3,4-二羟基呋喃-2-酮配合物。对C和C配合物与其他亲电试剂的反应性研究导致了不寻常的官能化反应：虽然烯酮羧酸盐C配合物与亲电试剂反应生成了新的多碳氧化配合物，但向乙炔二醇盐C配合物中添加CO导致形成了一种非常活泼的中间体，从而实现了芳族溶剂的C-H活化。这种独特的分子间反应性对应于由CO诱导的CO衍生配体前所未有的官能化。
