Construction of an organoruthenium complex (-[biphRuCp]PF_6-)) within a biphenylene-bridged inorganic-organic hybrid mesoporous material, and its catalytic activity in the selective hydrosilylation of 1-hexyne

摘要

An organoruthenium complex (-[biphRuCp]PF_6-); biph = -(C_6H_4)_2-, Cp = C_5H_5), constructed within a biphenylene-bridged inorganic-organic hybrid mesoporous material (HMM-biph) by use of a simple ligand-exchange reaction, has been used as a heterogeneous catalyst. UV-visible and X-ray absorption fine structure (XAFS) studies furnished evidence that the structure of the complex is closely similar to that of [(C_6H_6)RuCp]PF_6, suggesting that the biphenylene moiety within HMM-biph directly coordinates the metal center of the organoruthenium complex. The -[biphRuCp]PF_6-) complex constructed within the HMM-biph (HMM-biphRuCp) catalyzes hydrosilylation of 1-hexyne with triethylsilane in a solid-gas heterogeneous system and gives a-vinylsilane as a main product. Moreover, HMM-biphRuCp has higher catalytic activity than the -[phRuCp]PF_6-) (ph = -C_6H_4-) complex constructed within phenylene-bridged HMM (HMM- phRuCp). The high catalytic performance of HMM-biphRuCp can be attributed to the high loading of the HMM-biph with the Ru complex, because of the electrondonating ability of the biphenylene moieties.