Synthesis of tetra-pincer nickel(ii) and palladium(ii) complexes of resorcin[4]arene-octophosphinite [Res(OPR2)8] and rhodium-catalyzed regioselective hydroformylation reaction

Abstract

The condensation reaction of resorcinol with pentanal yielded resorcin[4]arene 1 which on bromination using N-bromosuccinimide at room temperature produced tetra-bromide derivative 2. The reactions of 2 with chlorodiphenylphosphine and o-phenylenephosphoro-chloridite yielded octaphosphinite 3 (hereafter referred to as octaphos) and octaphosphite 4, respectively. The reactions of 3 with Ni(COD)₂ or Pd₂(dba)₃·CHCl₃ in appropriate molar ratios yielded tetra-pincer complexes 5 and 6, respectively. The structures of both the complexes were established by single crystal X-ray diffraction studies. The resorcin[4]arene backbone adopts a boat structure in these complexes. Typically, the Rh-catalyzed hydroformylation of styrene prevalently delivers a branched (b) chiral aldehyde. A unique resorcin[4]arene skeleton based octaphos 3 was employed in the Rh-catalyzed hydroformylation of styrene. The hydroformylation of styrene with a metal to ligand ratio of 1 : 1 (M : L) was found to be regioselective, producing a linear (l) aldehyde as a major product with 100% conversion in 3 h. The l : b ratio surprisingly increased when the ortho positions of styrene were populated by methyl and chloro substituents. The hydroformylation of p-nitro styrene triggered a remarkably high linear : branched aldehyde ratio of 2.4 (71% linear aldehyde) despite its electron withdrawing nature. The highest linear selectivity of 97% (l : b ratio 27.8) was achieved in the case of 2,4,6-trimethylstyrene.