Coordination Behavior of a D‐Penicillaminato Aurate(I) Metalloligand Toward Coblat(III) Centers

Abstract

Abstract Treatment of (NH 4 )[Au(D‐Hpen‐ S ) 2 ](D‐H 2 pen = D‐penicillamine) with CoCl 2 ·6H 2 O in an acetate buffer solution, followed by air oxidation, gave neutral Au I Co III and anionic Au I 3 Co III 2 polynuclear complexes, [Au 3 Co 3 (D‐pen‐ N,O,S ) 6 ]([ 1 ]) and [Au 3 Co 2 (D‐pen‐ N,S ) 6 ] 3− ([ 2 ] 3− ), which were separated by anion‐exchange column chromatography. Complexes [ 1 ] and [ 2 ] 3− each formed a single isomer, and their structures were determined by single‐crystal X‐ray crystallography. In [ 1 ], each of three [Au(D‐pen‐ S ) 2 ] 3− metalloligands coordinates to two Co III ions in a bis‐tridentate‐ N,O,S mode to form a cyclic Au I 3 Co III 3 hexanuclear structure, in which three [Co(D‐pen‐ N,O,S ) 2 ] − octahedral units and six bridging S atoms adopt trans(O ) geometrical and R chiral configurations, respectively. In [ 2 ] 3− , each of three [Au(D‐pen‐ S ) 2 ] 3− metalloligands coordinates to two Co III ions in a bis‐bidentate‐ N,S mode to form a Au I 3 Co III 2 pentanuclear structure, in which two [Co(D‐pen‐ N,S ) 3 ] 3− units and six bridging S atoms adopt ∧ and R chiral configurations, respectively.