State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, 116023, Dalian, Liaoning, China.
University of Chinese Academy of Sciences, 100049, Beijing, China.
Nat Commun. 2019 Mar 1;10(1):996. doi: 10.1038/s41467-019-08804-y.
While numerous single atoms stabilized by support surfaces have been reported, the synthesis of in-situ reduced discrete metal atoms weakly coordinated and stabilized in liquid media is a more challenging goal. We report the genesis of mononuclear electron deficient Pt(0) by reducing HPtCl in liquid polydimethylsiloxane-polyethylene glycol (PDMS-PEG) (Pt@PDMS-PEG). UV-Vis, far-IR, and X-ray photoelectron spectroscopies evidence the reduction of HPtCl. CO infrared, and Pt and C NMR spectroscopies provide strong evidence of Pt(0), existing as a pseudo-octahedral structure of (ROR)Pt(0)ClH (R and R are H, C, or Si groups accordingly). The weakly coordinated (ROR)Pt(0)ClH structure and electron deficient Pt(0) have been validated by comparing experimental and DFT calculated Pt NMR spectra. The H in protic state and the Cl together resemble HCl as the weak coordination. Neutralization by a base causes the formation of Pt nanoparticles. The Pt@PDMS-PEG shows ultrahigh activity in olefin hydrosilylation with excellent terminal adducts selectivity.
虽然已经报道了许多由支撑表面稳定的单个原子，但在液体介质中合成原位还原的离散金属原子，这些原子弱配位且稳定，这是一个更具挑战性的目标。我们报告了通过在液体聚二甲基硅氧烷-聚乙二醇（PDMS-PEG）中还原 HPtCl 来生成单核缺电子 Pt(0)（Pt@PDMS-PEG）。紫外-可见、远红外和 X 射线光电子能谱证明了 HPtCl 的还原。CO 红外、Pt 和 C NMR 光谱提供了 Pt(0)的有力证据，其存在于（ROR）Pt(0)ClH 的拟八面体结构中（R 和 R 分别是 H、C 或 Si 基团）。弱配位的（ROR）Pt(0)ClH 结构和缺电子 Pt(0)通过比较实验和 DFT 计算的 Pt NMR 光谱得到了验证。质子状态的 H 和 Cl 共同类似于 HCl，作为弱配位。通过碱中和会导致 Pt 纳米颗粒的形成。Pt@PDMS-PEG 在烯烃硅氢化反应中表现出超高的活性，具有优异的末端加合物选择性。
