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Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2018-02-27 , DOI: 10.1021/jacs.7b11981
Jeffrey Camacho-Bunquin 1 , Magali Ferrandon 1 , Hyuntae Sohn 1 , Dali Yang 1 , Cong Liu 1 , Patricia Anne Ignacio-de Leon 2 , Frédéric A. Perras 3 , Marek Pruski 3, 4 , Peter C. Stair 1, 5 , Massimiliano Delferro 1
Affiliation  

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV-vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO2, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe3 with Zn(II)-modified SiO2 support is thermodynamically favorable (Δ G = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH3-TPD and DNP-enhanced 17O{1H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

中文翻译:

在 Zn(II) 改性二氧化硅上使用负载型有机铂 (IV) 催化剂进行化学选择性加氢

在室温下,在甲苯中通过表面有机金属化学将明确定义的有机铂 (IV) 位点接枝在 Zn(II) 改性的 SiO2 载体上。固态光谱包括 XAS、DRIFTS、DRUV-vis 和通过动态核极化 (DNP) 增强的固态 (SS) NMR,以及 TPR-H2 和 TEM 技术显示高度分散的(甲基环戊二烯基)甲基铂(IV)位点在表面 ((MeCp)PtMe/Zn/SiO2, 1)。此外,计算模型表明 (MeCp)PtMe3 与 Zn(II) 改性的 SiO2 载体的表面反应在热力学上是有利的(Δ G = -12.4 kcal/mol),这可能是由于羟基的酸度增加,如NH3-TPD 和 DNP 增强的 17O{1H} SSNMR 表明。原位 DRIFTS 和 XAS 氢化实验揭示了在 Pt-Me 基团氢解时可能形成表面 Pt(IV)-H。多相有机铂 (IV) 氢化物位点可催化 1,3-丁二烯选择性部分氢化为丁烯(高达 95%),并将硝基苯衍生物还原为苯胺(高达 99%),对还原敏感的官能团具有出色的耐受性基团(烯烃、羰基、腈、卤素)在温和的反应条件下。
更新日期:2018-02-27
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