SCS indenediide pincer complexes: Zr to Pd and Pt transmetallation

A new synthetic methodology based on transmetallation was developed for the preparation of SCS indenediide pincer complexes. Upon reaction of the 1,3-bis(thiophosphinoyle)indene 1 with [Zr(NMe2)(4)], C-sp3-H activation proceeds readily to give the new complex 2. Thermolysis at 100 degrees C for 5 h then affords the SCS pincer complex 3. Complex 2 can be stored under inert atmosphere for several weeks without decomposition. It is much more stable than 3 and was thus used as precursor to study transmetallation. Zr to Pd/Pt Transmetallation occurs rapidly and cleanly at room temperature. Accordingly, the pincer complexes 4, 5, 7 and 8 with triphenylphosphine or chloride as co-ligand were obtained in good to excellent yields under mild conditions. (C) 2016 Elsevier B.V. All rights reserved.