4.7 Article

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

Journal

DALTON TRANSACTIONS
Volume 51, Issue 26, Pages 9971-9977

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2dt01095j

Keywords

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Funding

  1. FundacAo de Amparo a Pesquisa do Estado de SAo Paulo (FAPESP) [2013/22160-0, 2017/06752-5, 2020/09280-0, 2021/06605-8]
  2. Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [307635/2018-0, 303809/2021-3]
  3. CoordenacAo de Aperfeicoamento de Pessoal de Nivel Superior - Brasil (CAPES) [001]
  4. FundacAo de Amparo a Pesquisa e InovacAo do Espirito Santo (FAPES) [174/2019]

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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.
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.

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