Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction

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.