Alkyne-Functionalized Ruthenium Nanoparticles: Impact of Metal

Nov 30, 2018 - Guangdong Engineering and Technology Research Center for Environmental Nanomaterials, School of Environment and Energy, South China ...
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Alkyne-functionalized ruthenium nanoparticles: impact of metal-ligand interfacial bonding interactions on the selective hydrogenation of styrene Fengqi Zhang, Jingjing Fang, Lin Huang, Wenming Sun, Zhang Lin, Zhenqing Shi, Xiongwu Kang, and Shaowei Chen ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b04028 • Publication Date (Web): 30 Nov 2018 Downloaded from http://pubs.acs.org on November 30, 2018

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Alkyne-Functionalized Ruthenium Nanoparticles: Impact of Metal-Ligand Interfacial Bonding Interactions on the Selective Hydrogenation of Styrene Fengqi Zhang†,a Jingjing Fang†,a Lin Huang†,a Wenming Sun,b Zhang Lin,c Zhenqing Shi c, Xiongwu Kang*a and Shaowei Chen*a,d a

Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China

b

State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100041, China c Guangdong

Engineering and Technology Research Center for Environmental Nanomaterials,

School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, China d Department

of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, United States * E-mails: [email protected]; [email protected] † equal contributing authors

ABSTRACT In the present study, ruthenium nanoparticles functionalized with terminal and internal alkynes were prepared and it was found that internal alkynes formed a η2 side-on configuration on ruthenium nanoparticles surface, in sharp contrast to the ruthenium-vinylidene interfacial bonds for terminal alkynes. For the nanoparticles capped with internal alkyne, hydrogenation of 1

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both the vinyl moiety and phenyl ring occurred, whereas selective hydrogenation of the vinyl moiety was observed with terminal alkyne-functionalized nanoparticles. This work highlights the importance of metal-organic interface in the rational design and engineering of nanoparticle catalyst for organic synthesis. KEYWORDS: ruthenium nanoparticles, internal alkyne, η2 side-on configuration, σ-π covalent, interfacial charge transfer, styrene hydrogenation

Introduction Catalysis plays a critical role in the production and transformation of valuable chemicals, where high selectivity towards desired molecules and compounds significantly reduces the amount of chemical wastes generated and represents an important part in the quest for “green chemistries”.1-4 Towards this end, a range of synthetic approaches based on nanotechnology have been reported in recent literatures.5 Among them, surface functionalization of transition metal nanoparticles by selecting organic capping ligands has been demonstrated to be a powerful tool in the manipulation and enhancement of the nanoparticle catalytic performance.6-11 For instance, as one of the capping ligands, terminal alkyne molecules have been demonstrated effective in modulating the catalytic activity of the metal nanoparticles in heterogeneous catalysis. For instance, rod-shaped [Au25(PPh3)10(C≡CPh)5X2]2+ (X = Br, Cl) nanoclusters exhibited selective catalytic activity towards the semi-hydrogenation of terminal alkynes, due to bridging of Au atoms by deprotonated alkynes, while the uncapped Au nanoclusters are active in the hydrogenation of both terminal and internal alkynes.12 In another study,13 the formation of surface staple motifs of PhC≡C−Au−C≡CPh in alkynyl-protected Au34Ag28(PhC ≡ C)34 nanoclusters led to enhanced catalytic performance towards the hydrolytic oxidation of organosilanes to silanols, in comparison to those with the surface ligands partially or completely 2

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ACS Catalysis

removed. Wang’s group compared the catalytic activity of alkyne- and thiolate-capped Au38 nanoclusters in the semi-hydrogenation of alkynes to alkenes and observed markedly higher activity of the former (>97%) than that of the latter (