Synthesis, Structure, Reactivity, and Catalytic Activity of Cyclometalated (Phosphine)‐ and (Phosphinite)ruthenium Complexes

摘要: Reactions of naphthyl- and o-methylphenyl-substituted phosphines with [RuCl2(p-cymene)]2 resulted in the corresponding phosphine-substituted ruthenium dichlorides (1a,b 3). When reactions aryl-substituted or phosphinites are carried out presence sodium acetate, cyclometalated to give five-membered metallacycle complexes (2a,b 4–6) through intramolecular activation a C(sp2)–H C(sp3)–H bond. Competition indicate that aromatic bond is more likely be activated than under same conditions, ring formed preference six-membered ring. The chemical reactivity 2a,b, two representatives cycloruthenated complexes, were explored, including conversion 1a,b substitution reaction η6-arene ligand 2a, synthesis bis(phosphine) complex starting from 2b, 2a diphenylacetylene. Besides, their catalytic activity on reduction ketones by transfer hydrogenation was also tested. molecular structures nine compounds, 1b, 4–10, determined single-crystal X-ray diffraction.