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Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction
Author(s) -
Lin PoYu,
Li DaiYing,
Ho FengHsien,
Liao JianHong,
Barik Subrat Kumar,
Liu C. W.
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201900086
Subject(s) - chemistry , nanoclusters , crystallography , ligand (biochemistry) , copper , hydride , cluster (spacecraft) , chalcogen , crystal structure , octahedron , stereochemistry , metal , organic chemistry , biochemistry , receptor , computer science , programming language
A structural study of ligand exchange on chalcogen‐passivated copper nanoclusters is far less developed. Herein, we report the synthesis of polyhydrido copper nanoclusters [Cu 20 H 11 {Se 2 P(O i Bu) 2 } 9 ] ( 2 ) passivated by Se‐donor ligands via ligand replacement reaction on [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] ( 1 ) with NH 4 [Se 2 P(O i Bu) 2 ]. In parallel to the synthesis of 2 , cluster [Cu 20 H 11 {S 2 P(CH 2 CH 2 Ph) 2 } 9 ] ( 4 ) was produced by the ligand exchange reaction on a new derivative of 1 , that is [Cu 20 H 11 {S 2 P(O n Pr) 2 } 9 ] ( 3 ). Solid state structures of both clusters 2 and 4 were unequivocally established by single‐crystal X‐ray diffraction studies and cluster 4 epitomizes exceptional case to preserve both the shape and size of the nanocluster during the course of ligand exchange. Structurally precise cluster 2 is the second example where the copper hydride nanocluster is stabilized by Se‐donor ligands. The anatomy of 2 can be visualized as a twisted cuboctahedral Cu 13 core, two triangular faces of which are capped by a Cu 6 cupola and a single Cu atom along the C 3 rotational axis.