Umehara Yoshihiko, Usui Ryosuke, Wada Yoshimasa, Sunada Yusuke
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8505, Japan.
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8505, Japan.
Commun Chem. 2023 May 15;6(1):93. doi: 10.1038/s42004-023-00892-8.
The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigation to clarify the preferences of these metal species with respect to the activation of Si-H and/or Si-Si bonds remain elusive. Here, we report that platinum(0) species that bear isocyanide or N-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph(H)SiSiPhSiPhSi(H)Ph in a stepwise manner, whereby the Si-Si bonds remain intact. In contrast, analogous palladium(0) species are preferably inserted into the Si-Si bonds of the same linear tetrasilane, whereby the terminal Si-H bonds remain intact. Substitution of the terminal hydride groups in Ph(H)SiSiPhSiPhSi(H)Ph with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt cluster.
过渡金属物种对有机硅化合物中Si-H键和/或Si-Si键的活化在功能有机硅化合物的制备中起着关键作用。尽管第10族金属物种经常用于活化Si-H键和/或Si-Si键，但迄今为止，关于这些金属物种在活化Si-H键和/或Si-Si键方面偏好的系统研究仍然难以捉摸。在此，我们报道了带有异腈或N-杂环卡宾（NHC）配体的铂（0）物种以逐步方式选择性地活化线性四硅烷Ph(H)SiSiPhSiPhSi(H)Ph的末端Si-H键，而Si-Si键保持完整。相比之下，类似的钯（0）物种更倾向于插入同一线性四硅烷的Si-Si键中，而末端Si-H键保持完整。用氯基团取代Ph(H)SiSiPhSiPhSi(H)Ph中的末端氢化物基团会导致铂（0）异腈插入所有Si-Si键中，从而得到一种前所未有的之字形Pt簇。
