三配位的Co(I)可生成不饱和二氢Co(III)和七配位的Co(V)。
Three-coordinate Co(I) provides access to unsaturated dihydrido-Co(III) and seven-coordinate Co(V).
作者信息
Ingleson Michael, Fan Hongjun, Pink Maren, Tomaszewski John, Caulton Kenneth G
机构信息
Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA.
出版信息
J Am Chem Soc. 2006 Feb 15;128(6):1804-5. doi: 10.1021/ja0572452.
The three-coordinate, T-shaped Co(I) complex, PNPCo (PNP = [(tBu2PCH2SiMe2)2N-], is readily synthesized by magnesium reduction of divalent PNPCoCl. Triplet (S = 1) PNPCo is coordinatively and electronically unsaturated and undergoes a thermally reversible oxidative addition reaction with H2, producing trivalent PNPCo(H)2. In contrast, the reaction with excess primary silane PhSiH3 quantitatively generates the base-stabilized silylene Co(V) compound {kappa2-tBu2PCH2Me2SiNSiMe2CH2tBu2P(H)Si=}Co(H)3(SiH2Ph)2.
三配位的T形钴（I）配合物PNPCo（PNP = [(tBu2PCH2SiMe2)2N-]）可通过二价PNPCoCl的镁还原轻松合成。三线态（S = 1）PNPCo在配位和电子方面不饱和，并与H2发生热可逆氧化加成反应，生成三价PNPCo(H)2。相比之下，与过量的伯硅烷PhSiH3反应可定量生成碱稳定的甲硅烯钴（V）化合物{κ2-tBu2PCH2Me2SiNSiMe2CH2tBu2P(H)Si=}Co(H)3(SiH2Ph)2。
Zotero 插件