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Updated: Jul 17, 2025

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
A binuclear guanidinate yttrium carbyne complex: unique reactivity toward unsaturated C-N, C-O and C-S bonds
Wen Jiang1, Feng Kong1, Iker Del Rosal2
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University 2005 Songhu Road, Jiangwan Campus Shanghai 200438 P. R. China lixinzh@fudan.edu.cn.
Abstract:
A guanidinato-stabilized binuclear yttrium carbyne complex [(PhCH2)2NC(NC6H3iPr2-2,6)2]2Y2(μ2-Me)(AlMe3)2(μ4-CH) (1) was synthesized via 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 S8. 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.
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