Construction of an organoruthenium complex (–[biphRuCp]PF6–) within a biphenylene-bridged inorganic–organic hybrid mesoporous material, and its catalytic activity in the selective hydrosilylation of 1-hexyne
作者:Masakazu Saito、Tetsuji Watanabe、Takashi Kamegawa、Yu Horiuchi、Masaya Matsuoka
DOI:10.1007/s11164-013-1460-1
日期:2014.1
An organoruthenium complex (–[biphRuCp]PF6–; biph = –(C6H4)2–, Cp = C5H5), 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 [(C6H6)RuCp]PF6, suggesting that the biphenylene moiety within HMM–biph directly coordinates the metal center of the organoruthenium complex. The –[biphRuCp]PF6– complex constructed within the HMM–biph (HMM–biphRuCp) catalyzes hydrosilylation of 1-hexyne with triethylsilane in a solid–gas heterogeneous system and gives α-vinylsilane as a main product. Moreover, HMM–biphRuCp has higher catalytic activity than the –[phRuCp]PF6– (ph = –C6H4–) 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 electron-donating ability of the biphenylene moieties.
一种有机钌络合物(-[biphRuCp]PF6-;biph = -(C6H4)2-, Cp = C5H5)被用作异相催化剂,该络合物是通过简单的配位交换反应在联苯桥接的无机-有机杂化介孔材料(HMM-biph)中构建的。紫外可见光和 X 射线吸收精细结构(XAFS)研究证明,该复合物的结构与[(C6H6)RuCp]PF6 的结构非常相似,这表明 HMM-biph 中的联苯分子直接配位了有机钌复合物的金属中心。在固气异构体系中,HMM-biph(HMM-biphRuCp)内构建的-[biphRuCp]PF6-复合物催化了 1-己炔与三乙基硅烷的氢硅化反应,并得到α-乙烯基硅烷作为主要产物。此外,与苯桥 HMM(HMM-phRuCp)中构建的-[phRuCp]PF6-(ph = -C6H4-)复合物相比,HMM-biphRuCp 具有更高的催化活性。HMM-biphRuCp 的高催化性能可归因于 HMM-biph 与 Ru 复合物的高负载,因为联苯分子具有电子负载能力。