The triphenylphosphine adduct of a copper(I) complex involving an incompletely bound N2S2 macrocyclic ligand

Abstract

The highly distorted tetrahedral copper(I) complex of the 14-membered trans-N₂S₂ macrocyclic ligand 6,7,15,16-tetrahydrodibenzo[f,m][1,8,4,11]dithiadiazacyclotetradecine (L) undergoes reaction with triphenylphosphine to form an adduct in which one of the two sulphur donors of the macrocycle has been displaced from the primary co-ordination sphere of the metal ion, resulting in tetrahedral co-ordination via an N₂PS donor array. The triphenylphosphine molecule is labile allowing the parent complex to be recovered upon recrystallization from an acetone–ethanol mixture. Crystal structures of both [CuL]ClO₄(1) and [CuL(PPh₃)]ClO₄·0.5Me₂CO (2) are reported. For (1): space group P6, a= 17.610(7), c= 5.377(2)Å, Z= 3, R= 0.061 for 947 ‘observed’ reflections. For (2): space group P, a= 15.74(2), b= 12.29(1), c= 9.91(1)Å, α= 82.07(9), β= 84.88(8), γ= 84.43(9)°, Z= 2, R= 0.10 for 1 796 ‘observed’ reflections. The solid-state ³¹P n.m.r. spectrum for (2) shows a quartet centred on 2.3 p.p.m. with line spacings of 1.41, 1.55, and 1.65 kHz.