Ishikawa Yuki, Kimura Seita, Yamamoto Koji, Murahashi Tetsuro
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan.
Chemistry. 2017 Oct 12;23(57):14149-14152. doi: 10.1002/chem.201703023. Epub 2017 Sep 18.
Though the M - or M face of palladium clusters may serve as the active binding site of substrates, it has been difficult to elucidate their substrate binding modes in solution. Here, it was proved that a soluble Pd - or Pd sheet cluster accommodates vinylarenes at its bridging coordination site in an unusual mode in palladium chemistry; that is, for the former, the coordination of the arene moiety precedes that of olefin moiety; for the latter, vinylarene coordinates to a distorted Pd sheet through oxidative π-addition of its styrene moiety.
尽管钯簇的M面或M面可能作为底物的活性结合位点，但在溶液中阐明它们的底物结合模式一直很困难。在此，已证明可溶性钯或钯片簇以钯化学中一种不寻常的模式在其桥连配位位点容纳乙烯基芳烃；也就是说，对于前者，芳烃部分的配位先于烯烃部分的配位；对于后者，乙烯基芳烃通过其苯乙烯部分的氧化π-加成与扭曲的钯片配位。
