Single step, high yield synthesis of para-hydroxy functionalized POCOP ligands and their Ni(ii) pincer derivatives

Abstract

The stoichiometric control of the reaction of phloroglucinol with different chlorophosphines ClPR 2 , R = iPr (1), tBu (2) or Ph (3), leads to the direct and high yield synthesis of the p-hydroxy functionalized POCOP ligands [C 6 H 3 -5-OH-1,3-(OPR 2 ) 2 ]. Typical reactions of these compounds with NiCl 2 Á6H 2 O provide a facile access to the corresponding POCOP pincer derivatives [NiCl{C 6 H 2 -4-OH-2,6-(OPR 2 ) 2 }], R = iPr (4), tBu (5) or Ph (6).

Synthesis, Characterisation and Hydrogen Bonding of Isostructural Group 10 Metal Halido Complexes Bearing a POCOP Ligand

“…The Ni1–I1 distance of 2.5252(3) Å is slightly longer than those of similar complexes with PPh 2 or P i Pr 2 donor sites [2.4976(3) and 2.492(1) Å,[7b] respectively], most likely due to the increased steric demand of the t Bu groups in complex 1‐I . Other than that, bond parameters resemble those found before for other related structures …”

Recent Advances on the Chemistry of POCOP–Nickel Pincer Compounds

“…5). The third method, although not in a single pot, offers, for the first time, the possibility of further functionalization at the aromatic moiety of the complexes obtained by introducing a -OH functionality at the para-position of the pincer complex [56]. This hydroxyl group can subsequently be derivatized with any of a variety of functionalities including groups that allow the POCOP-Ni complexes available to be supported on common polymeric supports.…”

A comparative study of the packing of two polymorphs of the nickel(II) pincer complex [2,6-bis(di-tert-butylphosphinoyl)-4-(3,5-dinitrobenzoyloxy)phenyl-κ3P,C1,P′]chloridonickel(II)

“…Ni II POCOP pincer complexes reported previously (García-Eleno et al 2015;Salah et al 2015). The conformational differences between the two polymorphs are reflected in the dihedral angles formed by the sixmembered arene rings.…”

“…The synthesis of the title compound was performed as reported previously (García-Eleno et al, 2015). A Schlenk flask with a rubber septum was charged with one equivalent of t BuPOCO t BuP dissolved in dry toluene (20 ml) and one equivalent of NiCl 2 Á6H 2 O.…”