Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Dalton Trans. 2019 Dec 3;48(47):17655-17659. doi: 10.1039/c9dt04307a.
The construction of fluorocarbene ligands within the coordination sphere of transition metal complexes using sequential nucleophilic and electrophilic addition to a vinylidene complex is described. Reaction of [Ru(η5-C5H5)(dppe)([double bond, length as m-dash]C[double bond, length as m-dash]CPhF)][N(SO2Ph)2] with [NMe4]F results in nucleophilic attack of fluoride at the metal-bound carbon of the vinylidene ligand to give alkenyl complex [Ru(η5-C5H5)(dppe)(-CF[double bond, length as m-dash]CFPh)]. Subsequent eletrophilic fluorination with N-fluorobenzenesulfonimide (NFSI) results in the formation of the fluorinated carbene complex [Ru(η5-C5H5)(dppe)([double bond, length as m-dash]CF-CHFPh)][N(SO2Ph)2]. The fluorocarbene complexes undergo rearrangement to liberate free fluorinated alkenes, a process governed by the choice of solvent and anion, representing a new metal-mediated route to fluorinated alkenes from alkynes.
描述了在过渡金属配合物的配位球内用顺序亲核和亲电加成反应构建氟卡宾配体的方法。[Ru(η5-C5H5)(dppe)([double bond, length as m-dash]C[double bond, length as m-dash]CPhF)][N(SO2Ph)2]与[NMe4]F 反应导致氟离子在乙烯基配体的金属结合碳上进行亲核攻击，得到烯基配合物[Ru(η5-C5H5)(dppe)(-CF[double bond, length as m-dash]CFPh)]。随后用 N-氟代苯磺酰亚胺 (NFSI) 进行亲电氟化反应，形成氟化卡宾配合物[Ru(η5-C5H5)(dppe)([double bond, length as m-dash]CF-CHFPh)][N(SO2Ph)2]。氟卡宾配合物发生重排以释放游离的氟化烯烃，该过程受溶剂和阴离子的选择控制，代表了一种从炔烃到氟化烯烃的新的金属介导途径。
