Department of Chemistry, Tsinghua University, Beijing, 100084, People's Republic of China.
Inorg Chem. 2012 Jun 4;51(11):6020-31. doi: 10.1021/ic2024378. Epub 2012 May 14.
(Ni(1-x),Mg(x))(3)Si(2)O(5)(OH)(4) solid-solution nanotubes (NTs) with tunable compositions were hydrothermally synthesized by altering the molar ratio of Mg(2+) to Ni(2+). The as-synthesized NTs were loaded with sub-0.06 wt % palladium (Pd; ∼0.045 wt %) for Suzuki-Miyaura (SM) coupling reactions between iodobenzene or 4-iodotoluene and phenylboronic acid. The (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) NTs supported by 0.045 wt % Pd promoted the iodobenzene-participated coupling reaction with a high yield of >99%, an excellent recycling catalytic performance during 10 cycles of catalysis with yields of ∼99%, and also an extremely low Pd releasing level of ∼0.02 ppm. High-activity Pd and PdO clusters, multitudes of dislocations, and defects and terraces contained within the NTs should contribute to the (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) NTs supported by 0.045 wt % Pd as a robust, reusable, and high-efficiency catalyst for SM coupling reactions with an extremely low Pd releasing level. The present hydrothermally stable (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) solid-solution silicate NTs provided an ideal alternative tubular-structured support for noble- or transition-metal catalysts with low Pd loading, good recycling, and extremely low ppb levels of Pd release, which could also be extended to some other SM coupling reactions.
具有可调组成的(Ni(1-x),Mg(x))(3)Si(2)O(5)(OH)(4) 固溶体纳米管(NTs)通过改变 Mg(2+)与 Ni(2+)的摩尔比水热合成。将合成的 NTs 负载 0.06wt%以下的钯(Pd;约 0.045wt%),用于碘苯或 4-碘甲苯与苯硼酸的 Suzuki-Miyaura(SM)偶联反应。(Ni,Mg)(3)Si(2)O(5)(OH)(4)(Mg(2+):Ni(2+) = 1.0:1.0)NTs 负载 0.045wt%Pd 促进了碘苯参与的偶联反应,产率高达>99%,在 10 次催化循环中具有优异的循环催化性能,产率约为 99%,Pd 释放水平也极低,约为 0.02ppm。高活性的 Pd 和 PdO 簇、大量位错和缺陷以及 NTs 中的平台,都有助于(Ni,Mg)(3)Si(2)O(5)(OH)(4)(Mg(2+):Ni(2+) = 1.0:1.0)NTs 负载 0.045wt%Pd 作为一种用于 SM 偶联反应的坚固、可重复使用和高效催化剂,Pd 释放水平极低。本研究中,水热稳定的(Ni,Mg)(3)Si(2)O(5)(OH)(4)(Mg(2+):Ni(2+) = 1.0:1.0)固溶体硅酸盐 NTs 为负载量低、可回收、Pd 释放量低至 ppb 级的贵金属或过渡金属催化剂提供了理想的管状结构载体,该方法也可扩展到其他一些 SM 偶联反应中。