化学
磷化矿
镍
氧化加成
氧化磷酸化
立体化学
有机化学
生物化学
催化作用
作者
Quinton J. Bruch,Noah D. McMillion,Chun-Hsing Chen,Alexander J. M. Miller
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2023-01-24
卷期号:62 (5): 2389-2393
被引量:1
标识
DOI:10.1021/acs.inorgchem.2c04188
摘要
Oxidative addition is an essential elementary reaction in organometallic chemistry and catalysis. While a diverse array of oxidative addition reactions has been reported to date, examples of P-O bond activation are surprisingly rare. Herein, we report the ligand-templated oxidative addition of a phosphinite P-O bond in the diphosphinito aniline compound HN(2-OPiPr2-3,5-tBu-C6H2)2 [H(P2ONO)] at Ni0 to form (PONO)Ni(HPiPr2) after proton rearrangement. Notably, the P-O cleavage occurs selectively over an amine N-H bond activation. Additionally, the ligand cannibalization is reversible, as addition of XPR2 (X = Cl, Br; R = iPr, Cy) to (PONO)Ni(HPiPr2) readily produces either symmetric or unsymmetric (P2ONO)NiX species and free HPiPr2. Finally, the mechanisms of both the initial P-O bond cleavage and its subsequent reconstruction are investigated to provide further insight into how to target P-O bond activation.
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