Copper(II) Thiaethyneporphyrin and Copper(II) 21-phosphoryl N-confused Porphyrin Hybrids. Intramolecular Copper(II)-carbon Interaction Inside of a Porphyrinoid Surrounding

Stabilization of unusual organocopper(II) species via the very efficient protection of the copper(II)-carbon bond has been achieved encapsulating the copper(II) center in the coordination core of suitably constructed carbaporphyrinoids. Copper(II) was inserted into hybrid N-confused porphyrins which contain 21-diphenylphosphoryl-, 21-diphenylthiophosphoryl-, or 21-phosphinodithioic substituents or into 20-thiaethyneporphyrin, an aromatic porphyrinoid, which combines two structural motifs of 21-thiaporphyrin and ethyne. Two distinctly different types of the copper(II)-carbon bond have been detected. Copper(II) hybrid N-confused porphyrins reveal the η(1)-C(21) side-on coordination. The unprecedented equatorial metal(II)···η(2)-CC interaction has been trapped in a copper(II) thiaethyneporphyrin surrounding.