Department of Chemistry, University of Alberta, 11227 Saskatchewan Dr., Edmonton, Alberta, T6G 2G2, Canada.
Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan.
Chemistry. 2018 Sep 25;24(54):14392-14399. doi: 10.1002/chem.201802958. Epub 2018 Sep 3.
The introduction of the labile trimethylsiloxy group to Ge centers in the presence of an N-heterocyclic carbene donor is reported. The new complex IPr⋅GeCl(OSiMe ) (IPr=[(HCNDipp) C:]; Dipp=2,6-iPr C H ) was readily converted into the structurally unique Ge siloxy(hydrido)germylene IPr⋅GeH(OSiMe )⋅BH by treatment with lithium borohydride. Additionally, the reactive siloxygermylene cation [IPr⋅Ge(OSiMe )] was synthesized and clean oxidative addition of CH Cl was demonstrated. The two-coordinate [IPr⋅Ge(OSiMe )] cation also promoted the catalytic hydroborylation of sterically hindered ketones under mild conditions, with enhanced reactivity stemming from an open coordination site at Ge.
本文报道了在 N-杂环卡宾供体存在的情况下，将不稳定的三甲硅氧基基团引入锗中心。新的配合物 IPr⋅GeCl(OSiMe )（IPr=[(HCNDipp) C:]; Dipp=2,6-iPr C H ）很容易通过与硼氢化锂反应转化为结构独特的锗硅氧基（氢）亚基锗 IPr⋅GeH(OSiMe )⋅BH。此外，还合成了反应性的硅锗亚基阳离子[IPr⋅Ge(OSiMe )]，并证明了它与 CH Cl 的清洁氧化加成。二配位的[IPr⋅Ge(OSiMe )]阳离子也能在温和条件下促进位阻酮的催化硼氢化反应，其反应性的增强源于 Ge 上的开放配位位。
