Double and Reversible Alkyl Transfer from ZrBn₄/HfBn₄ to a Diiminepyridine Ligand

Abstract

Reaction of MBn 4 (M = Zr, Hf ) with diiminepyridine ligands Me DIP, Et DIP and iPr DIP [ R DIP = 2,6-(2,6-R 2 C 6 H 3 N=CMe) 2 -C 5 H 3 N] results in the transfer of two benzyl groups to the DIP imine carbon atoms, generating mixtures of rac and meso isomers of [ R DIP + 2Bn]MBn 2 . The diastereomers could in several cases be separated by fractional crystallization, and the X-ray structures of rac and meso [ Et DIP + 2Bn]ZrBn 2 , meso-[ Me DIP + 2Bn]ZrBn 2 and meso-[ Et DIP + 2Bn]HfBn 2 are reported.

Diiminepyridine‐Supported Phosphorus(I) and Phosphorus(III) Complexes: Synthesis, Characterization, and Electrochemistry

“…Diiminepyridines (DIPs, Figure ) are among the most popular redox “non‐innocent” ligands, so‐called as the ligand can serve as an additional site for oxidation/reduction events in metal coordination complexes . In addition to widespread application in late, first‐row transition metal mediated catalysis, they are also used for their simple ability to bind early transition metals,, rare earths, and main‐group elements in a tridentate, pincer‐like fashion . With respect to the p‐block, DIP complexes are known for Groups 13, 14,, 15 and 16, centres.…”