Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state 31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea (HL)

A new complex of N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)2 (HL) of formula [(Cu3L3)2] has been synthesized and characterized by single crystal X-ray diffraction, FT-IR, 1H, 31P NMR in solution and by 31P CPMAS NMR spectroscopy in the solid state. A comparison of the structure and the spectral parameters of [(Cu3L3)2] with those of the mononuclear analogue [Cu(PPh3)2L] was performed. In the solid state the aggregate [(Cu3L3)2] represents the first example of a spontaneous “side-by-side” association of two neutral cyclic [Cu3L3] moieties using two Cu–S–Cu bridges formed by the sulfur atoms of the PS-groups. The values of the 1J(31P–63,65Cu) and 2J(31P–31P) coupling constants of the [Cu(PPh3)2]+ moiety in the solid state spectra are reported.

Graphical abstractNew N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)2 (HL) chelates of the CuI cation of type [(Cu3L3)2] have been synthesized and characterized by single crystal X-ray diffraction, FT-IR, 1H, 31P NMR in solution and by CPMAS 31P NMR spectroscopy in the solid state. In the solid state the aggregate [(Cu3L3)2] represents the first example of a spontaneous “side-by-side” association of two neutral cyclic [Cu3L3] moieties using two Cu–S–Cu bridges formed by the sulfur atoms of the PS-groups. A comparison of the structure and the spectral parameters of [(Cu3L3)2] with those of the mononuclear analogue [Cu(PPh3)2L] was performed. The values of the 1J(31P–63,65Cu) and 2J(31P–31P) coupling constants of the [Cu(PPh3)2]+ moiety in the solid state spectra are reported.Figure optionsDownload full-size imageDownload as PowerPoint slide