The preparation and characterisation of a series of group IV metallocene dithiolato complexes containing a naphthalene backbone

Reduction of the sulfur–sulfur bond of naphtho[1,8-cd]-1,2-dithiole with 2 equivalents of Li(BEt)3H to give the dilithium salt followed by the addition of an equivalent of bis(pentamethyl)metallocene dichloride [(Cp)2∗MCl2,M=Ti,Zr,Hf,Cp∗=C5Me5] gives the sulfur bonded complexes (Cp)2∗TiS2C10H6(1),(Cp)2∗ZrS2C10H6(2)and(Cp)2∗HfS2C10H6(3) containing six-membered MS2C3 rings. The products were obtained in moderate yield as crystals and have been fully characterised and had their X-ray crystal structures determined.

Graphical abstractMetathesis reactions lead to (Cp)2∗MS2C10H6[M=Ti,Zr,Hf] which are isomorphous allowing a comparison of the structural parameters.Figure optionsDownload full-size imageDownload as PowerPoint slide