Pinacho-Olaciregui Jokin, Verde-Sesto Ester, Taton Daniel, Pomposo José A
Centro de Física de Materiales (CSIC - UPV/EHU) - Materials Physics Center MPC, P° Manuel Lardizabal 5, E-20018 Donostia, Spain.
Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux INP-ENSCBP, 16 av. Pey Berland, 33607 Pessac cedex, France.
Nanoscale. 2024 May 23;16(20):9742-9747. doi: 10.1039/d4nr01261e.
Heterobimetallic Pt(II)/Cu(II) single-chain polymer nanoparticles (SCNPs) were sequentially synthesized from a polymeric precursor featuring both α-diazo-β-ketoester and naked β-ketoester functional groups. Photoactivated carbene generation at = 365 nm from α-diazo-β-ketoester moieities was triggered for bonding Pt(II) ions from dichloro(1,5-cyclooctadiene)Pt(II) to the polymeric precursor, whereas Cu(II) ions were subsequently incorporated Cu(II)-(β-ketoester) complex formation using Cu(II) acetate. Both intrachain Pt(II) bonding and Cu(II) complexation were found to contribute to the folding of the polymeric precursor generating Pt(II)/Cu(II)-SCNPs as evidenced by infrared spectroscopy, size exclusion chromatography and dynamic light scattering. These heterobimetallic SCNPs proved highly efficient as soft nanocatalysts for the consecutive one-pot alkyne semihydrogenation/alkene dioxygenation reactions at room temperature in -butylpyrrolidone, as a non-toxic alternative solvent to ,-dimethylformamide.
异双金属Pt(II)/Cu(II)单链聚合物纳米颗粒（SCNPs）是由一种同时具有α-重氮-β-酮酯和裸露的β-酮酯官能团的聚合物前体依次合成的。在365nm波长下，α-重氮-β-酮酯基团发生光活化卡宾生成反应，促使二氯(1,5-环辛二烯)Pt(II)中的Pt(II)离子与聚合物前体结合，随后利用醋酸铜通过形成Cu(II)-(β-酮酯)配合物引入Cu(II)离子。红外光谱、尺寸排阻色谱和动态光散射表明，链内Pt(II)键合和Cu(II)络合都有助于聚合物前体折叠生成Pt(II)/Cu(II)-SCNPs。这些异双金属SCNPs被证明是高效的软纳米催化剂，可在室温下于N-丁基吡咯烷酮（作为N，N-二甲基甲酰胺的无毒替代溶剂）中连续进行一锅法炔烃半氢化/烯烃双氧化反应。
