Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates

Kairui Liu; Guangjin Hou; Jingbo Mao; Zhanwei Xu; Peifang Yan; Huixiang Li; Xinwen Guo; Shi Bai; Z Conrad Zhang

doi:10.1038/s41467-019-08804-y

Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates

Nat Commun. 2019 Mar 1;10(1):996. doi: 10.1038/s41467-019-08804-y.

Authors

Kairui Liu^{1

2}, Guangjin Hou¹, Jingbo Mao^{1

3}, Zhanwei Xu¹, Peifang Yan¹, Huixiang Li¹, Xinwen Guo³, Shi Bai^{4

5}, Z Conrad Zhang⁶

Affiliations

¹ 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.
² University of Chinese Academy of Sciences, 100049, Beijing, China.
³ State Key Laboratory of Fine Chemicals, PSU-DUT Joint Centre for Energy Research, School of Chemical Engineering, Dalian University of Technology, 116024, Dalian, China.
⁴ Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716, USA. bais@udel.edu.
⁵ State Key Laboratory of Applied Organic Chemistry, Lanzhou University, 730000, Lanzhou, Gansu, China. bais@udel.edu.
⁶ 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. zczhang@dicp.ac.cn.

Abstract

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 Pt₁(0) by reducing H₂PtCl₆ in liquid polydimethylsiloxane-polyethylene glycol (PDMS-PEG) (Pt₁@PDMS-PEG). UV-Vis, far-IR, and X-ray photoelectron spectroscopies evidence the reduction of H₂PtCl₆. CO infrared, and ¹⁹⁵Pt and ¹³C NMR spectroscopies provide strong evidence of Pt₁(0), existing as a pseudo-octahedral structure of (R¹OR²)₂Pt(0)Cl₂H₂ (R¹ and R² are H, C, or Si groups accordingly). The weakly coordinated (R¹OR²)₂Pt(0)Cl₂H₂ structure and electron deficient Pt₁(0) have been validated by comparing experimental and DFT calculated ¹⁹⁵Pt 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 Pt₁@PDMS-PEG shows ultrahigh activity in olefin hydrosilylation with excellent terminal adducts selectivity.

Publication types

Research Support, Non-U.S. Gov't

Grants and funding

P30 GM110758/GM/NIGMS NIH HHS/United States