Copper(I) complexes of a thioether-functionalized short-bite aminobis(phosphonite), [PhN{P(–OC10H6(μ-S)C10H6O–)}2]

Abstract Copper(I) complexes of short-bite aminobis(phosphonite), PhN{P(–OC 10 H 6 (μ-S)C 10 H 6 O–)} 2 ( 1 ) have been synthesized. Reactions of 1 with an excess of CuX (X = Cl, Br, and I) afforded the ligand-bridged binuclear complexes, [PhN(PR- κP ) 2 {Cu(μ-X)(MeCN)} 2 ] ( 2 , X = Cl; 3 , X = Br; 4 , X = I; R = –OC 10 H 6 (μ-S)C 10 H 6 O–), whereas treatment with 0.5 equiv. of [Cu(MeCN) 4 ]PF 6 produces the mononuclear bischelated cationic complex, [{PhN(PR- κP ) 2 } 2 Cu](PF 6 ) ( 5 ). Single crystal X-ray structures of complexes 3 and 4 are reported. Complex 3 shows strong π–π stacking interactions between the naphthyl moieties, whereas complex 4 shows ligand-supported Cu⋯Cu metallophilic interactions.