Redox potentials of a series of bis(2,4-pentanedionato)cobalt(III) complexes containing amine, phosphine, arsine, or their hybrid donor didentate ligands. σ and π contributions in the CoIII-N, -P and -As bonding

Masakazu Kita, Kazuo Kashiwabara

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Reduction (E1/2(red)) and oxidation potentials (E1/2(ox)) of [Co(acac)2(L)]+ (acac=2,4-pentanedionate) complexes containing an N-N, N-N′, N′-N′, N-P, P-P, N-As, or As-As′ didentate ligand as L(N = -CH2NH2; N′ = -CH2NMe2; P = -CH2PMe2; As′ = -CH2AsMe2; As′ = -CH2CH2AsMe2) were determined by electrochemical measurements. The E1/2(red) values which reflect the dσ*(Co) orbital (homo) energy shift negatively in the following order: (i) L = N′-N′ > N′-N > N-N; (ii) L = N′-N > As-N > P-N; and (iii) L = N′-N′ > As-As′ > P-P. The E1/2(ox) values shift positively in the following order : L = P-P, As-As′ <P-N, As-N <N-N, N-N′, N′-N′. This order suggests that the dπ(Co) orbital is more destabilized by the phosphine or arsine ligands than the amine ones.

Original languageEnglish
Pages (from-to)2771-2775
Number of pages5
JournalPolyhedron
Volume16
Issue number16
Publication statusPublished - 1997
Externally publishedYes

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phosphine
Cobalt
phosphines
Oxidation-Reduction
Amines
amines
cobalt
Ligands
orbitals
ligands
shift
Oxidation
oxidation
arsine
energy

Keywords

  • σ and π contributions
  • Co-N,-P and -As bonding
  • Geometry of donor groups
  • Ligand field strength
  • Redox potentials of Co complexes
  • Trans influence

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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title = "Redox potentials of a series of bis(2,4-pentanedionato)cobalt(III) complexes containing amine, phosphine, arsine, or their hybrid donor didentate ligands. σ and π contributions in the CoIII-N, -P and -As bonding",
abstract = "Reduction (E1/2(red)) and oxidation potentials (E1/2(ox)) of [Co(acac)2(L)]+ (acac=2,4-pentanedionate) complexes containing an N-N, N-N′, N′-N′, N-P, P-P, N-As, or As-As′ didentate ligand as L(N = -CH2NH2; N′ = -CH2NMe2; P = -CH2PMe2; As′ = -CH2AsMe2; As′ = -CH2CH2AsMe2) were determined by electrochemical measurements. The E1/2(red) values which reflect the dσ*(Co) orbital (homo) energy shift negatively in the following order: (i) L = N′-N′ > N′-N > N-N; (ii) L = N′-N > As-N > P-N; and (iii) L = N′-N′ > As-As′ > P-P. The E1/2(ox) values shift positively in the following order : L = P-P, As-As′ <P-N, As-N <N-N, N-N′, N′-N′. This order suggests that the dπ(Co) orbital is more destabilized by the phosphine or arsine ligands than the amine ones.",
keywords = "σ and π contributions, Co-N,-P and -As bonding, Geometry of donor groups, Ligand field strength, Redox potentials of Co complexes, Trans influence",
author = "Masakazu Kita and Kazuo Kashiwabara",
year = "1997",
language = "English",
volume = "16",
pages = "2771--2775",
journal = "Polyhedron",
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T1 - Redox potentials of a series of bis(2,4-pentanedionato)cobalt(III) complexes containing amine, phosphine, arsine, or their hybrid donor didentate ligands. σ and π contributions in the CoIII-N, -P and -As bonding

AU - Kita, Masakazu

AU - Kashiwabara, Kazuo

PY - 1997

Y1 - 1997

N2 - Reduction (E1/2(red)) and oxidation potentials (E1/2(ox)) of [Co(acac)2(L)]+ (acac=2,4-pentanedionate) complexes containing an N-N, N-N′, N′-N′, N-P, P-P, N-As, or As-As′ didentate ligand as L(N = -CH2NH2; N′ = -CH2NMe2; P = -CH2PMe2; As′ = -CH2AsMe2; As′ = -CH2CH2AsMe2) were determined by electrochemical measurements. The E1/2(red) values which reflect the dσ*(Co) orbital (homo) energy shift negatively in the following order: (i) L = N′-N′ > N′-N > N-N; (ii) L = N′-N > As-N > P-N; and (iii) L = N′-N′ > As-As′ > P-P. The E1/2(ox) values shift positively in the following order : L = P-P, As-As′ <P-N, As-N <N-N, N-N′, N′-N′. This order suggests that the dπ(Co) orbital is more destabilized by the phosphine or arsine ligands than the amine ones.

AB - Reduction (E1/2(red)) and oxidation potentials (E1/2(ox)) of [Co(acac)2(L)]+ (acac=2,4-pentanedionate) complexes containing an N-N, N-N′, N′-N′, N-P, P-P, N-As, or As-As′ didentate ligand as L(N = -CH2NH2; N′ = -CH2NMe2; P = -CH2PMe2; As′ = -CH2AsMe2; As′ = -CH2CH2AsMe2) were determined by electrochemical measurements. The E1/2(red) values which reflect the dσ*(Co) orbital (homo) energy shift negatively in the following order: (i) L = N′-N′ > N′-N > N-N; (ii) L = N′-N > As-N > P-N; and (iii) L = N′-N′ > As-As′ > P-P. The E1/2(ox) values shift positively in the following order : L = P-P, As-As′ <P-N, As-N <N-N, N-N′, N′-N′. This order suggests that the dπ(Co) orbital is more destabilized by the phosphine or arsine ligands than the amine ones.

KW - σ and π contributions

KW - Co-N,-P and -As bonding

KW - Geometry of donor groups

KW - Ligand field strength

KW - Redox potentials of Co complexes

KW - Trans influence

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