Title : Observation of an organic acid mediated spin state transition in a Co(II)-Schiff base complex: an EPR, HYSCORE, and DFT study.

Pub. Date : 2012 Aug 6

PMID : 22830538






8 Functional Relationships(s)
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1 The interactions of a weak organic acid (acetic acid, HOAc) with a toluene solution of the Co(II)-Schiff base type complex, (R,R")-N,N"-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II) (labeled [Co(1)]), was investigated using EPR, HYSCORE, and DFT computations. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
2 The interactions of a weak organic acid (acetic acid, HOAc) with a toluene solution of the Co(II)-Schiff base type complex, (R,R")-N,N"-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II) (labeled [Co(1)]), was investigated using EPR, HYSCORE, and DFT computations. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
3 The interactions of a weak organic acid (acetic acid, HOAc) with a toluene solution of the Co(II)-Schiff base type complex, (R,R")-N,N"-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II) (labeled [Co(1)]), was investigated using EPR, HYSCORE, and DFT computations. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
4 The newly formed LS state is assigned to the coordinated [Co(II)(1)]-(HOAc) complex, possessing a z(2), (2)A(1)) ground state (species A; g(x) = 2.42, g(y) = 2.28, g(z) = 2.02, A(x) = 100, A(y) = 120, A(z) = 310 MHz). Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
5 This complex is tentatively assigned to a paramagnetic superoxo bridged dimer (AcO(-))[Co(II)(1) O(2)(-)Co(III)(1)](HOAc), as distinct from the more common diamagnetic peroxo bridged dimers. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
6 Species C is characterized by a very broad HS EPR signal (g(x) = 5.1, g(y) = 3.9, g(z) = 2.1) and is reversibly formed by oxygenation of the LS [Co(II)(1)]-(HOAc) complex to the superoxo complex [Co(III)(1)O(2)(-)](HOAc), which subsequently forms the association complex C by interaction with the HS [Co(II)(1)](OAc(-)) species. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
7 Species C is characterized by a very broad HS EPR signal (g(x) = 5.1, g(y) = 3.9, g(z) = 2.1) and is reversibly formed by oxygenation of the LS [Co(II)(1)]-(HOAc) complex to the superoxo complex [Co(III)(1)O(2)(-)](HOAc), which subsequently forms the association complex C by interaction with the HS [Co(II)(1)](OAc(-)) species. Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens
8 Overall, it appears that a facile interconversion of the [Co(1)] complex, possessing a LS ground state, occurs in the presence of acetic acid, producing both HS and LS Co(II) states, prior to formation of the oxidized active form of the catalyst, [Co(III)(1)](OAc(-)). Acetic Acid mitochondrially encoded cytochrome c oxidase II Homo sapiens