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Platinum nanoparticles stabilized by N-heterocyclic thiones. Synthesis and catalytic activity in mono- and di-hydroboration of alkynes
Nanoscale ( IF 5.8 ) Pub Date : 2020/03/17 , DOI: 10.1039/d0nr00251h Leonardo C. Moraes 1, 2, 3, 4, 5 , Rute C. Figueiredo 1, 2, 3, 4, 6 , Juan P. Espinós 2, 4, 7, 8, 9 , Florencia Vattier 2, 4, 7, 8, 9 , Antonio Franconetti 4, 10, 11, 12 , Carlos Jaime 4, 10, 11, 12 , Bertrand Lacroix 4, 13, 14, 15, 16 , Javier Rojo 1, 2, 3, 4 , Patricia Lara 1, 2, 3, 4, 5 , Salvador Conejero 1, 2, 3, 4, 5
Nanoscale ( IF 5.8 ) Pub Date : 2020/03/17 , DOI: 10.1039/d0nr00251h Leonardo C. Moraes 1, 2, 3, 4, 5 , Rute C. Figueiredo 1, 2, 3, 4, 6 , Juan P. Espinós 2, 4, 7, 8, 9 , Florencia Vattier 2, 4, 7, 8, 9 , Antonio Franconetti 4, 10, 11, 12 , Carlos Jaime 4, 10, 11, 12 , Bertrand Lacroix 4, 13, 14, 15, 16 , Javier Rojo 1, 2, 3, 4 , Patricia Lara 1, 2, 3, 4, 5 , Salvador Conejero 1, 2, 3, 4, 5
Affiliation
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N-Heterocyclic Thiones (NHT) proved to be efficient ligands for the stabilization of small platinum nanoparticles (1.3–1.7 nm), synthesized by decomposition of [Pt(dba)2], under a H2 atmosphere, in the presence of variable sub-stoichiometric amounts of the NHT. Full characterization by means of TEM, HR-TEM, NMR, ICP, TGA and XPS have been carried out, providing information about the nature of the metal nanoparticles and the interaction of the NHT ligands to the metal surface. Importantly, DFT calculations indicate that some NHT ligands interact with the metal through the C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C double bond of the imidazole fragment in addition to the sulfur atom, thus providing additional stabilization to the nanoparticles. According to XPS, TGA and ICP techniques, the surface coverage by the ligand increases by decreasing the size of the substituents on the nitrogen atom. The platinum nanoparticles have been used as catalyst in the hydroboration of alkynes. The most active system is that with a less covered surface area lacking an interaction of the ligand by means of the CC double bond. This catalyst hydroborates alkynes with excellent selectivities towards the monoborylated anti-Markovnikov product (vinyl-boronate) when one equiv. of borane is used. Very interestingly, aliphatic alkynes undergo a second hydroborylation process leading to the corresponding 1,1- and 1,2-diboroylated species with good selectivities towards the former.
中文翻译：
通过N杂环硫酮稳定的铂纳米颗粒。炔烃的单氢和双氢硼化反应的合成及催化活性
N-杂环亚硫醚（NHT）被证明是稳定小铂纳米颗粒（1.3-1.7 nm）的有效配体，该小纳米颗粒是在H 2气氛下，在存在可变亚原子的情况下通过分解[Pt（dba）2 ]合成的化学计量的NHT。已经通过TEM，HR-TEM，NMR，ICP，TGA和XPS进行了全面表征，从而提供了有关金属纳米粒子的性质以及NHT配体与金属表面相互作用的信息。重要的是，DFT计算表明某些NHT配体通过C与金属相互作用除硫原子外，咪唑片段的C双键，从而为纳米粒子提供额外的稳定性。根据XPS，TGA和ICP技术，通过减小氮原子上取代基的大小，配体的表面覆盖率会增加。铂纳米颗粒已经用作炔烃的硼氢化反应的催化剂。最活跃的系统是表面积较小的体系，缺乏配体通过C的相互作用C双键。当一当量时，该催化剂对单硼化的抗马氏尼可夫产物（乙烯基硼酸酯）具有极好的选择性的硼氢化炔烃。使用硼烷。非常有趣的是，脂族炔烃经历了第二次加氢硼化过程，生成了相应的1,1-和1,2-二硼烷基化物质，对前者具有良好的选择性。
更新日期：2020-03-27
C double bond of the imidazole fragment in addition to the sulfur atom, thus providing additional stabilization to the nanoparticles. According to XPS, TGA and ICP techniques, the surface coverage by the ligand increases by decreasing the size of the substituents on the nitrogen atom. The platinum nanoparticles have been used as catalyst in the hydroboration of alkynes. The most active system is that with a less covered surface area lacking an interaction of the ligand by means of the CC double bond. This catalyst hydroborates alkynes with excellent selectivities towards the monoborylated anti-Markovnikov product (vinyl-boronate) when one equiv. of borane is used. Very interestingly, aliphatic alkynes undergo a second hydroborylation process leading to the corresponding 1,1- and 1,2-diboroylated species with good selectivities towards the former.
中文翻译：
通过N杂环硫酮稳定的铂纳米颗粒。炔烃的单氢和双氢硼化反应的合成及催化活性
N-杂环亚硫醚（NHT）被证明是稳定小铂纳米颗粒（1.3-1.7 nm）的有效配体，该小纳米颗粒是在H 2气氛下，在存在可变亚原子的情况下通过分解[Pt（dba）2 ]合成的化学计量的NHT。已经通过TEM，HR-TEM，NMR，ICP，TGA和XPS进行了全面表征，从而提供了有关金属纳米粒子的性质以及NHT配体与金属表面相互作用的信息。重要的是，DFT计算表明某些NHT配体通过C与金属相互作用
除硫原子外，咪唑片段的C双键，从而为纳米粒子提供额外的稳定性。根据XPS，TGA和ICP技术，通过减小氮原子上取代基的大小，配体的表面覆盖率会增加。铂纳米颗粒已经用作炔烃的硼氢化反应的催化剂。最活跃的系统是表面积较小的体系，缺乏配体通过C的相互作用C双键。当一当量时，该催化剂对单硼化的抗马氏尼可夫产物（乙烯基硼酸酯）具有极好的选择性的硼氢化炔烃。使用硼烷。非常有趣的是，脂族炔烃经历了第二次加氢硼化过程，生成了相应的1,1-和1,2-二硼烷基化物质，对前者具有良好的选择性。
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