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 η1-C­(21) side-on coordination. The unprecedented equatorial metal­(II)···η2-CC interaction has been trapped in a copper­(II) thiaethyneporphyrin
surrounding.