Jiang Wen, Kong Feng, Del Rosal Iker, Li Meng, Wang Kai, Maron Laurent, Zhang Lixin
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University 2005 Songhu Road, Jiangwan Campus Shanghai 200438 P. R. China
LPCNO, Université de Toulouse 31077 Toulouse France
Chem Sci. 2023 Aug 3;14(34):9154-9160. doi: 10.1039/d3sc03483f. eCollection 2023 Aug 30.
A guanidinato-stabilized binuclear yttrium carbyne complex [(PhCH)NC(NCHPr-2,6)]Y(μ-Me)(AlMe)(μ-CH) (1) was synthesized C-H bond activation and its versatile reactivities were investigated. Complex 1 underwent σ-bond metathesis with PhSSPh and nucleophilic addition with PhCN to form the corresponding yttrium thiolate complex 3 and aza-allyl complex 4 respectively. Additionally, the rare yttrium carbide complex 5 was also prepared by treatment of complex 1 with S. Interestingly, in the reaction with PhNCS, the C[double bond, length as m-dash]S double bond was cleaved, followed by C-H bond activation to give the yttrium sulfide complex 7 with a ketenimine dianion ligand. Unexpectedly, the reaction of complex 1 with CO (1 atm) resulted in deoxygenative coupling of CO, to afford mono- or dioxo-yttrium complexes at different temperatures. The mechanism of the possible formation processes of complexes 3 and 9 was elucidated by DFT calculations.
合成了一种胍基稳定的双核钇卡宾配合物[(PhCH)NC(NCHPr-2,6)]Y(μ-Me)(AlMe)(μ-CH) (1)，并研究了其C-H键活化及其多种反应活性。配合物1与PhSSPh发生σ键复分解反应，与PhCN发生亲核加成反应，分别形成相应的硫醇钇配合物3和氮杂烯丙基配合物4。此外，还通过用S处理配合物1制备了罕见的碳化钇配合物5。有趣的是，在与PhNCS的反应中，C=S双键被裂解，随后发生C-H键活化，得到带有烯酮亚胺双阴离子配体的硫化钇配合物7。出乎意料的是，配合物1与CO(1 atm)的反应导致CO的脱氧偶联，在不同温度下生成单氧或双氧钇配合物。通过密度泛函理论(DFT)计算阐明了配合物3和9可能的形成过程机理。
