Insertion of CS2 into Ag–S bonds. Preparations and crystal structures of[{[Ag(SC6H2Pri3-2,4,6)]4·CHCl3}n] and its insertion product with CS2, [{Ag(S2CSC6H2Pri3-2,4,6)}2{Ag(SC6H2Pri3-2,4,6)}6]·8CHCl3

Abstract

By the use of a sterically hindered arenethiolate ligand, 2,4,6-Prⁱ₃C₆H₂SH the colourless silver thiolate complex [{[Ag(SC₆H₂Prⁱ₃-2,4,6)]₄·CHCl₃}_n](1) has been synthesized and structurally characterized. The structure of (1) consists of a one-dimensional double (Ag–SR)_n strand belt polymer. The strand (Ag–SR)_n is formed by alternating silver and sulphur atoms of the ligands. Complex (1) reacts with a small amount of CS₂ to give a pale yellow product [{Ag(S₂CSC₆H₂Prⁱ₃-2,4,6)}₂{Ag(SC₆H₂Prⁱ₃-2,4,6)}₆]·8CHCl, (2), and CS₂ is inserted into a quarter of the Ag–S bonds of complex (1). The unusual structure ofcomplex (2) consists of eight coplanar silver atoms linked through arenethiolate (RS) and aryl thiocarbonate (RSCS₂) ligands, exhibiting a number of interesting features. A novel structural type of insertion of CS₂ into M–S bonds has been found. Crystal data: (1), triclinic, space group P, a= 14.443(7), b= 16.201 (1 2), c= 16.586(14)Å, α= 68.27(6),β= 80.84(6), γ= 75.73(5)°, for Z= 2, R= 0.074, for 2 065 observed reflections; (2), monoclinic, space group P2₁/n, a= 17.897(7), b= 27.131(18), c= 19.111(9)Å, β= 113.59(3)°, for Z= 2, R= 0.084, for 3 930 observed reflections.