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 language | English |
|---|---|
| Pages (from-to) | 2771-2775 |
| Number of pages | 5 |
| Journal | Polyhedron |
| Volume | 16 |
| Issue number | 16 |
| Publication status | Published - 1997 |
| Externally published | Yes |
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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
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. / Kita, Masakazu; Kashiwabara, Kazuo.
In: Polyhedron, Vol. 16, No. 16, 1997, p. 2771-2775.Research output: Contribution to journal › Article
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TY - JOUR
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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M3 - Article
VL - 16
SP - 2771
EP - 2775
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 16
ER -