1

Xiao-Li PEI Researcher ID: I-7875-2016 Date of birth: 6th Nov 1988 Nationality: Chinese Email: pei@chem.s.u-tokyo.ac.jp> URL for web site: http://www.researcherid.com/rid/I-7875-2016

EDUCATION � 2010/9-2015/6 PhD in Physical Chemistry

College of Chemistry and Chemical Engineering, Xiamen University (Fujian, China) Thesis title: “Study on Auration of Small-molecules C-H/N-H Bonds with Oxo-Au(I)-Ag(I) Clusters” Supervisor: Prof. Quan-Ming Wang

� 2006/9-2010/6 B.S. in Applied Chemistry College of Science, Huazhong Agricultural University (Wuhan, China) Thesis title: “Study on Synthesis and Biological Activity of N'-(2-methoxyphenyl)-N-nitro-N-(2,6-dibromo-4-fluorophenyl)urea” Thesis Advisor: Prof. Changshui Chen

� 2008/3-2010/6 B.S. in Pharmacy (Secondary Major) College of Pharmaceutical Sciences, Wuhan University (Wuhan, China) Thesis title: “Study on Preparation of Modified Pachymaran as Amphiphilic Molecules Nanometer Microballoons and Its Capability as Drug Carrier” Thesis Advisor: Assoc. Prof. Yuling Xiao

CURRENT POSITION 2017/5/16-now Postdoctoral researcher in Prof. Shionoya´s Group, Department of Chemistry, Graduate School of Science, The University of Tokyo, Japan

PREVIOUS POSITIONS � 2016/9/1-2019/2/28: Postdoctoral Researcher

Prof. Antonio M. Echavarren´s Group, Institute of Chemical Research of Catalonia (ICIQ), Spain � 2015/12-2016/8: Research Assistant

State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Fujian, China Prof. Quan-Ming Wang´s Group

� 2015/1-2015/12: Civil Servant Guigang Food and Drug Administration, Guangxi, China

FELLOWSHIPS 2017/2-2019/2 H2020-MSCA-ITN-2016: Marie Skłodowska-Curie Individual Fellowships 2013/8 National Scholarship for PhD students, Xiamen University 2012/4 Si-Min Wu Scholarship for postgraduate students, Xiamen University 2008/11 Syngenta Scholarship for undergraduates, Huazhong Agricultural University 2007/11 National Grant for undergraduates, Huazhong Agricultural University

PUBLICATIONS [1] X.-L. Pei, Y. Yang, Z. Lei, S.-S. Chang, Z.-J. Guan, X.-K. Wan, T.-B. Wen, Q.-M. Wang*. Highly

Active Gold(I)-Silver(I) Oxo Cluster Activating sp3 C-H Bonds of Methyl Ketones under Mild Conditions. J. Am. Chem. Soc. 2015, 137, 5520-5525.

[2] X.-L. Pei, Y. Yang, Z. Lei, Q.-M. Wang*. Geminal Tetraauration of Acetonitrile: Hemilabile-Phosphine-Stabilized Au8Ag4 Cluster Compounds. J. Am. Chem. Soc. 2013, 135, 6435-6437.

2

[3] C. García-Morales, X.-L. Pei, J. M. Sarria Toro, A. M. Echavarren*. Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions. Angew. Chem., Int. Ed. 2019, just accepted, doi.org/10.1002/anie.201814577.

[4] Z. Lei, X.-L. Pei, Z.-J. Guan, Q.-M. Wang*. Full Protection of Intensely Luminescent Gold(I)-Silver(I) Cluster by Phosphine Ligands and Inorganic Anions. Angew. Chem., Int. Ed. 2017, 12, 7117-7120. (Hot paper, Inside Back Cover.)

[5] Z. Lei, X.-L. Pei, Z. G. Jiang, Q.-M. Wang*. Cluster Linker Approach: Preparation of a Luminescent Porous Framework with NbO Topology by Linking Silver Ions with Gold(I) Clusters. Angew. Chem., Int. Ed. 2014, 53, 12771-12775. (Inside Back Cover.)

[6] Y. Yang, X.-L. Pei, Q.-M. Wang*. Postclustering Dynamic Covalent Modification for Chirality Control and Chiral Sensing. J. Am. Chem. Soc. 2013, 135, 16184-16191.

[7] Z. Lei, Z.-J. Guan, X.-L. Pei, S.-F. Yuan, X.-K. Wan, J.-Y. Zhang, Q.-M. Wang*. Atomic Precise Au10Ag2 Nanocluster with Red-NIR Dual Emission. Chemistry - A European Journal 2016, 22, 11156-11160.

[8] Y. Yang, J.-H. Jia, X.-L. Pei, H. Zheng, Z.-A. Nan, Q.-M. Wang*. Diastereoselective Synthesis of O Symmetric Heterometallic Cubic Cages. Chem. Commun. 2015, 51, 3804-3807.

[9] X.-L. Pei, E. S. Smirnova, A. Pereira, A. M. Echavarren*. Catalytically Active Hexanuclear Gold and Gold–Silver Clusters via C–Si Auration. 2019, Manuscript in preparation.

ATTENDANCE TO CONFERENCES � ICIQ-INTECAT School, December 11-13, 2018, Tarragona, Spain

Oral Presentation: From Mono- to Bi-metallic Catalysts: Anionic-Arylphosphines-Stabilized Small Gold and Gold-Silver Clusters

� GOLD 2018, July 15-18, 2018, Paris, France Oral Presentation: Anionic-Arylphosphines-Stabilized Small Gold and Gold-Silver Clusters: From Mono- to Bi-metallic Catalysts

� XVI Biennial Meeting - Spanish Royal Society of Chemistry (RSEQ), June 25-29, 2017, Sitges, Spain Poster: Silver Doping in Hexanuclear Gold(I) Clusters Stabilized by Hemilabile Phosphine

PARTICIPATION IN FUNDED PROJECTS � Polynuclear Gold Cluster Catalysis H2020-MSCA-ITN-2016 (Grant Agreement: 747170-XiaoLi Pei)

Host: Prof. Antonio M. Echavarren´s Group, Institute of Chemical Research of Catalonia (ICIQ), Spain � The design, structure and property of cluster compounds (Grant No. 21125102), supported by Natural

Science Foundation of China. PI: Prof. Quan-Ming Wang

� Functionalization of cluster compounds by post-clustering modification (Grant No. 21473139), supported by Natural Science Foundation of China. PI: Prof. Quan-Ming Wang

RESEARCH INTERESTS AND EXPERTISES � Rational design and synthesis of phosphine ligands; � Synthesis of ligand-protected homo-/hetero-coinage metallic clusters; � Single crystals growth and X-ray diffraction structural analysis; � Luminescence and catalysis.

DESCRIPTION OF PREVIOUS RESEARCH ACHIEVEMENTS o Geminal Tetraauration of Acetonitrile: Hemilabile-Phosphine-Stabilized Au8Ag4 Cluster

Compounds. (J. Am. Chem. Soc. 2013, 135, 6435-6437.) This work showed that oxonium gold(I)-silver(I) clusters can fully deprotonate acetonitrile at room temperature, leading to unprecedented tetra-auration of acetonitrile with the assistance of a protic solvent. The unique crystal structures have been confirmed by X-ray crystallography diffraction. A concerted metallation/deprotonation process for the C−H activation of acetonitrile was proposed, indicating that the

3

oxo ion plays a key role in the C−H activation of acetonitrile, and this provides new insight in terms of the involvement of Ag2O in gold-catalyzed processes.

Scheme 1. (a) Centrosymmetric structure of [(CCN)2Au8Ag4(dppy)8(CH3CN)2]6-; (b) possible transition state of the

auration of acetronitrile; (c) the formation of water monitored by 1H NMR spectra.

o Highly Active Gold(I)-Silver(I) Oxo Cluster Activating sp3 C-H Bonds of Methyl Ketones under Mild Conditions. (J. Am. Chem. Soc. 2015, 137, 5520-5525.) This work reported a highly oxo-gold(I)-silver(I) cluster protected by hemilabile phosphine ligands [OAu3Ag3(PPhpy2)3](BF4)4 can activate C(sp

3)-H bonds under mild conditions for a broad scope of methyl ketones(as shown in below). Activation happens via triple deprotonation of the methyl group, leading to formation of heterometallic Au(I)−Ag(I) clusters RCOCAu4Ag4(PPhpy2)4(BF4)5 (PPhpy2 = bis(2-pyridyl)phenylphosphine), which have been confirmed by X-ray crystallography diffraction. The real activator can be formed in-situ by [OAu3Ag(PPhpy2)3](BF4)2 with 2 equiv. of AgBF4. The oxo ion and the metal centers are found to be essential in the cleavage of sp3 C−H bonds of methyl ketones. The scope shows an interesting selectivity of activation: C-H bonds in –COCH3 rather than N-H bond in –NH2 or O−H bond in –OH, and the terminal methyl group is preferred over secondary or tertiary sp3 C−H bonds. This work highlights the powerful reactivity of metal clusters toward C−H activation and sheds new light on gold(I)-mediated catalysis.

Scheme 2. Illustration of C-H bonds activation in various methyl ketones by oxonium gold(I)-silver(I) cluster

[OAu3Ag3(PPhpy2)3](BF4)4 under mild conditions.

Scheme 3. Crystal structures of cation parts in [RCOCAu4Ag4(PPhpy2)4(BF4)5].

4

o Catalytically Active Hexanuclear Gold and Gold–Silver Clusters via C–Si Auration. (X.-L. Pei, E. S. Smirnova, A. Pereira, A. M. Echavarren*, 2019, Manuscript in preparation.) The design of atomically precise gold clusters as catalysts is of great importance in understanding of catalytic process at the atomic level. Here, for the first time, C–Si auration (Au(I)/Si transmetalation) has been applied in the construction of gold and gold–silver clusters with phosphine ligands stabilized by 3c–2e Au–C–M bonds. Hexanuclear gold clusters [Au6L4](SbF6)2 are obtained by reaction of (L-TMS)AuCl with AgSbF6, whereas reaction (L-TMS)AuCl with AgSbF6 and Ag2O leads to gold–silver clusters [Au4Ag2L4](SbF6)2. Other [Au5], [Au4Ag], [Au2] and [Au12Ag4] clusters can also be obtained by this C–Si auration process. An oxo-trigold(I) intermediate has been identified as the intermediate in the formation of the silver–doped clusters. An interesting configuration rearrangement of a [Au4Ag2L](SbF6)2 cluster triggered by the addition of acetone as a coordinating solvent has been observed. Clusters containing ¨PAu–Au*–AuP¨ (Au*: the active gold center) as the structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.

Figure 2. Gold(I) and gold(I)-silver(I) clusters formed via Au(I)/Si transmetallation and structure-related studies in gold-

catalyzed reactions.