Litcius/Paper detail

Reactivities of Interstitial Hydrides in a Cu<sub>11</sub> Template: En Route to Bimetallic Clusters

Rhone P. Brocha Silalahi, Qi Wang, Jian‐Hong Liao, Tzu‐Hao Chiu, Ying‐Yann Wu, Xiaoping Wang, Samia Kahlal, Jean‐Yves Saillard, C. W. Liu

2021Angewandte Chemie International Edition39 citationsDOIOpen Access PDF

Abstract

Abstract In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable Cu I dihydride template [Cu 11 H 2 {S 2 P(O i Pr) 2 } 6 (C≡CPh) 3 ] ( H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(O i Pr) 2 } 6 (C≡CPh) 3 ] + ( 1 ), [AgH 2 Cu 14 {S 2 P(O i Pr) 2 } 6 ((C≡CPh) 6 ] + ( 2 ), and [AuCu 11 {S 2 P(O i Pr) 2 } 6 (C≡CPh) 3 Cl] ( 3 ). Compounds 1 and 2 are both M I species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal‐pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed‐valent [AuCu 11 ] 10+ metal core, making it a two‐electron superatom.

Topics & Concepts

Bimetallic stripHydrideSuperatomCrystallographyChemistryMetalIonOpen shellNeutron diffractionCrystal structureElectronic structureComputational chemistryOrganic chemistryNanocluster Synthesis and ApplicationsMetal-Organic Frameworks: Synthesis and ApplicationsAsymmetric Hydrogenation and Catalysis