Discrete Silver(I)‐Palladium(II)‐Oxo Nanoclusters, {Ag4Pd13} and {Ag5Pd15}, and the Role of Metal–Metal Bonding Induced by Cation Confinement. Issue 51 (29th November 2016)

• Record Type: Journal Article
• Authors: Yang, Peng; Xiang, Yixian; Lin, Zhengguo; Lang, Zhongling; Jiménez‐Lozano, Pablo; Carbó, Jorge J.; Poblet, Josep M.; Fan, Linyuan; Hu, Changwen; Kortz, Ulrich
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 51(2016)
• Page Start: 15766
• Page End: 15770
• Publication Date: 2016-11-29
• Subjects: DFT -- metal-metal bonding -- palladium -- polyoxometalates -- silver; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201608122
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We introduce the class of discrete silver(I)‐palladium(II)‐oxo nanoclusters with the preparation of {Ag4 Pd13 } and {Ag5 Pd15 }. Both polyanions represent the first examples of noble metal‐capped polyoxo‐noble‐metalates in a fully inorganic assembly, featuring an unprecedented host–guest mode containing hetero‐ and homometallic Ag–Pd and Ag–Ag bonding interactions. Comprehensive theoretical calculations suggest that the Ag–Pd metallic bonds originate partially from surface confinement of Ag I guest ions onto the anionic polyoxopalladate host that is induced by strong electrostatic forces. This work opens the field of fully inorganic silver‐palladium‐oxo nanoclusters, which can be considered as discrete mixed noble metal precursors for the formation of monodisperse core–shell nanoparticles, with high relevance for catalysis. Abstract : Mixed precious metal clusters : The two discrete silver(I)‐palladium(II)‐oxo nanoclusters, {Ag4 Pd13 } and {Ag5 Pd15 }, are the first examples of noble metal‐capped polyoxo‐noble‐metalates, featuring an unprecedented host–guest bonding mode comprising hetero‐ and homometallic Ag–Pd and Ag–Ag bonding interactions. Theoretical calculations suggest that the Ag–Pd metallic bonds originate partially from surface confinement that is induced by strong electrostatic forces.