Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Abstract

Photochemical reactions of diruthenium tetrahydride complexes containing cyclopentadienyls as auxiliary ligands, CpsRu(μ-H)4RuCps (1) (a: Cps = C5Me5 (Cp*), b: C5EtMe4 (CpEt), and c: 1,2,4-C5(t-Bu)3H2 (Cp‡)), with tetrahydrofuran were studied for elucidation of the reaction mode of dinuclear complexes containing multiple bridging hydrides. Complexes 1a–c reacted with tetrahydrofuran under UV irradiation (365 nm) to produce bridging cyclic Fischer-type carbene complexes, {CpsRu(μ-H)}2(μ-cyclo-CCH2CH2CH2O−)(μ-H)2 (5), via consecutive C–H bond cleavage at the α-position of the oxygen atom. The characteristic cyclic structures of the bridging carbene ligands were unambiguously confirmed by X-ray diffraction studies. Line-shape analysis of the variable-temperature 1H NMR spectra of 5c demonstrated the rotation of the bridging carbene ligand.