Abstract
The salicylidene Schiff bases of bis(2‐aminophenyl)diselenide and ‐ditelluride react with [MIICl2(PPh3)2] (M = Ni, Pt) or [PdII(OAc)2(PPh3)2] with formation of square‐planar complexes with the general formulae [MII(LY)(PPh3)] (M = Ni, Pd, Pt, Y = Se, Te). The ligands coordinate to the metals as tridentate {O,N,Se/Te} chelates. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh3 ligands. A mechanism for such reactions has been derived from the experimental data with the aid of DFT calculations. It suggests a higher polarization of the dichalcogenide bond with partial charge separation upon coordination to a metal centre, which therefore facilitates the cleavage of the dichalcogenide bond with PPh3. In accordance with the proposed mechanism, best yields are obtained with a strict exclusion of oxygen, but in the presence of water.
Highlights
The interest in the chemistry of the nickel, palladium and platinum triad is fueled by the manifold of catalytic properties of their complexes and their biological activities
We demonstrate that the method used for high-valent rhenium complexes can be extended to the metals nickel, palladium and platinum
The shielding of the chalcogen atoms decreases in the order Pd > Ni > Pt, which has been observed in Schiff base selenolato complexes before.[23]
Summary
The interest in the chemistry of the nickel, palladium and platinum triad is fueled by the manifold of catalytic properties of their complexes and their biological activities. The formation of adducts, the oxidation of the ligands to the dichalcogenides and the reduction of the metal ions occurs mainly for the tellurolato complexes. The yield of [PdII(LY)(PPh3)] increased to the range of 80 % by the addition of water to the reaction mixture.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
