Substitution reactions on a hypercoordinated main-group element encapsulated in a pentacapped trigonal prismatic copper cage

Abstract

Compound 1, [Cu₁₁(μ₉-Br)(μ₃-Br)₃{S₂P(OⁱPr)₂}₆]⁺, containing the first μ₉-bromide at the center of a pentacapped trigonal-prismatic copper skeleton, was isolated from the reaction of [Cu(CH₃CN)₄](PF₆), NH₄[S₂P(OⁱPr)₂], and Bu₄NBr in 11 : 6 : 4 ratios in methanol. Treatment of 1 with Bu₄NI resulted in a complete replacement of four bromides to yield a corresponding iodo analogue {Cu₁₁(I)(I)₃[S₂P(OⁱPr)₂]₆}⁺, 2. The central bromide and iodide in 1 and 2 can be replaced by a sulfide generated in situ from Na₂S₂O₃ to produce [Cu₁₁(μ₉-S)(μ₃-X)₃{S₂P(OⁱPr)₂}₆] (X = Br, 3; I, 4)_. All four compounds displayed interesting photoluminescent properties.