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 |
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Pages (from-to) | 2771-2775 |
Number of pages | 5 |
Journal | Polyhedron |
Volume | 16 |
Issue number | 16 |
DOIs | |
Publication status | Published - Jan 1 1997 |
Externally published | Yes |
Keywords
- Co-N,-P and -As bonding
- Geometry of donor groups
- Ligand field strength
- Redox potentials of Co complexes
- Trans influence
- σ and π contributions
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry