Ni(II) and Cu(III) organometallic complexes of trans doubly N-confused porphodimethenes: Synthesis, spectroscopic and theoretical characterization

The first ever spectroscopic and theoretical report of a distorted square planar Ni(II) organometallic complex via one inner CH activation and a weak Ni-C bond with C-H agostic interaction and near square planar organometallic Cu(III) complex via double inner CH activation of trans doubly N-confused oxocalix[4]phyrin are reported. Synthesis, spectroscopic and theoretical investigations of hitherto unknown highly stable nickel, and copper organometallic complexes of trans-doubly N-confused porphodimethenes are reported. The distorted square planar Ni organometallic complex has been susceptible to trivial +2 oxidation state of Ni via single CH activation and another weak Ni-C bond with C-H agostic interaction while the diamagnetic near square planar copper complex exhibits the atypical +3 oxidation state of copper via double inner CH activation. The conformational preorganization and metallation induced conformational reorganization owing to the formation of M-C bond formations by both nickel and copper have been thoroughly investigated by various spectroscopic techniques and in-depth DFT level theoretical calculations.