A synthetic tactic to substitute axial ligands in sterically demanding Ru(ii)porphyrinates

Author(s)

Fontana, Liniquer A. ; Rigolin, Vitor H. ; Ribeiro, Marcos A. ; Barros, Wdeson P. ; Megiatto, Jackson D., Jr.

• Document type: Journal article
• Source: DALTON TRANSACTIONS; v. 51, n. 26, p. 7-pg., 2022-06-16.

Abstract

We report a synthetic strategy that allows for the preparation of sterically encumbered heteroleptic Ru(ii)porphyrinates with the desired configuration of stable/inert and weak/labile axial ligands to direct reactions between substrates to exclusively occur at the sterically encumbered face. To demonstrate the method, we describe the synthesis of a strapped-Ru(ii)porphyrinate bearing a stable/inert triphenylphosphine (PPh3) bulky axial ligand coordinated exo to the central cavity and a weak/labile methanol molecule coordinated at the internal axial position. With this axial ligand configuration, the reported Ru(ii)porphyrinate exclusively promotes carbene transfer reactions to olefins through the central cavity, which has been verified by the selective formation of cycloprane-linked [2]rotaxanes. (AU)

• FAPESP's process: 17/06752-5 - Development of New Template Strategies for the Synthesis of Polyrotaxanes
• Grantee: Liniquer André Fontana
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers
• Grantee: Jackson Dirceu Megiatto Junior
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 20/09280-0 - The study of magnetic, luminescent, photoreactive, and redox properties of polynuclear molecular systems containing transition and lanthanide metal ions
• Grantee: Wdeson Pereira Barros
• Support Opportunities: Regular Research Grants
• FAPESP's process: 21/06605-8 - Systems chemistry: controlling the complex behavior of mixtures of interacting molecules to develop molecular machines, interlocked polymers and new materials
• Grantee: Jackson Dirceu Megiatto Junior
• Support Opportunities: Research Grants - Young Investigators Grants - Phase 2