Electron donor-acceptor properties of porphyrins, phthalocyanines, and related ring chelates: A molecular orbital approach

C. Fierro, Alfred B. Anderson, Daniel Alberto Scherson

研究成果: Article

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Tetraazaporphyrin is used as a primitive fragment to examine theoretically the electron donor-acceptor properties of a variety of highly conjugated planar ligands of the porphyrin and phthalocyanine type. Calculations employing the atom superposition electron delocalization MO theory indicate that for iron macrocycles the energy gap between the occupied dxz, dyz orbitals and the empty eg(π*) ring orbitals plays a key role in controlling the extent of metal to ring back-bonding. This provides a framework for a rational search of structural modifications of chelating ligands that may afford an optimized activation of axially coordinated π electron acceptor molecules such as dioxygen, nitric oxide, and carbon monoxide. The higher reactivity of iron(II) porphyrins toward such π acceptor species, compared to iron(II) phthalocyanine, is attributed to the longer Me-N bond length in the porphyrins, which leads to less metal to ligand back-bonding and thus to more electron charge at the metal center.

元の言語English
ページ(範囲)6902-6907
ページ数6
ジャーナルJournal of physical chemistry
92
発行部数24
DOI
出版物ステータスPublished - 1988 1 1
外部発表Yes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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