The preparation and characterisation of rhodium(III) and Iridium(III) half sandwich complexes with napthalene-1,8-dithiolate, acenaphthene-5,6-dithiolate and biphenyl-2,2′-dithiolate

•Full spectral and crystallographic characterisation of a new dithiol compound.•Crystallographic studies of dithiol ligands and precursor complexes.•Synthesis of half sandwich Rh and Ir dithiolato complexes by metathesis.•Full spectral and crystallographic characterisation of all half sandwich complexes.

The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp*M(PEt3) (S-R-S)], M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (NaphthS2, a), acenaphthene-5,6-dithiolate (AcenapS2, b) and biphenyl-2,2′-dithiolate (BiphenS2, c) is reported. We also describe the isolation of a new compound acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spectroscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H2a), acenaphthene-1,8-dithiol (H2b), 1,1′-biphenyl-2,2′-dithiol (H2c) and benzene-1,2-dithiol (H2d) have also been characterised by single crystal X-ray diffraction.

Graphical abstractA series of “piano stool” type rhodium and iridium complexes have been prepared using simple dithiols without the need for base. A Cp* ring caps the complex while a neutral phosphine donor fills the vacant coordination site.Figure optionsDownload full-size imageDownload as PowerPoint slide