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Isolation and Structural Elucidation of 15‐Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two‐Electron Copper Superatom
Author(s) -
Chakrahari Kiran Kumarvarma,
Liao Jingping,
Silalahi Rhone P. Brocha,
Chiu TzuHao,
Liao JianHong,
Wang Xiaoping,
Kahlal Samia,
Saillard JeanYves,
Liu C. W.
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202002544
Subject(s) - chemistry , phenylacetylene , copper , crystallography , cluster (spacecraft) , crystal structure , superatom , icosahedral symmetry , electronic structure , computational chemistry , organic chemistry , computer science , programming language , catalysis
Abstract Highly reactive copper‐dihydride clusters, [Cu 15 (H) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ](PF 6 ) {R = n Bu ( 1 H ), n Pr ( 2 H ), i Bu ( 3 H )}, are isolated during the reaction of [Cu 28 H 15 {S 2 CN n Bu 2 } 12 ](PF 6 ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two‐electron superatom [Cu 13 (S 2 CNR 2 ) 6 (C 2 Ph) 4 ] + . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH 3 CN) 4 ](PF 6 ), BH 4 − and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu 15 (D) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ] + , and a single‐crystal neutron structure of 2 H . Structural characterization of 1 H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH 2 ) − unit. Reaction of 3 H with Au(I) salts yields a highly luminescent [AuCu 12 (S 2 CN i Bu 2 ) 6 (C 2 Ph) 4 ] + cluster.