Complexes of cobalt(III) with phenolate-containing polydentate ligands and bovine serum apo-transferrin

Towards creating spectroscopic models for cobalt(III)-tyrosinate interactions

Musa S. Shongwe, Said K M Al-Hatmi, Helder M. Marques, Rachel Smith, Ryoji Nukada, Masahiro Mikuriya

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Abstract

Reaction of each member of a series of variously substituted N-(2-hydroxybenzyl)glycinate (hbg 2-) ligands [5-bromo- (5-Br-hbg 2-); 5-chloro- (5-Cl-hbg 2-); 3,5-dichloro- (3,5-Cl 2-hbg 2-); 5-chloro-3-methyl- (5,3-Cl,Me-hbg 2-); and 3,5-dimethyl- (3,5-Me 2-hbg 2-)] with cobalt(II) in stoichiometric amounts under ambient conditions afforded the Co III complex anions of the general formulatrans,trans,trans-[Co(hbg) 2] -. Single-crystal X-ray analyses of [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Cl 2-hbg) 2]3 and [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Me 2-hbg) 2]5 {[C 5H 10- NH 2] piperidinium counter ion} have revealed similar structural motifs of these compounds. Each of the crystal structures shows two non-equivalent complex anions in the unit cell connected through hydrogen bondingvia the piperidinium cation. The two hbg 2- ligands in each complex ion are arranged facially around the cobalt(III) ion and each ligand employs a phenolate oxygen, an amine nitrogen and a carboxylate oxygen to form a distorted octahedral geometry with C i symmetry. These compounds (1-5) serve as spectroscopic models for the interaction of cobalt(III) with tyrosinate ligands. The electronic spectrum of the compound [C 5H 10NH 2]-trans,trans,trans-[Co(5,3-Cl, Me-hbg) 2]4 bears a striking resemblance to that of the complex of cobalt(III) with bovine serum transferrin, [Co 2BTf]. In contrast to previous studies on the spectroscopy of the transferrins, one of the two ligand-field transitions expected to occur in [Co 2BTf] is evident in the electronic spectrum of this derivative of bovine serum transferrin in vitro. One of the fascinating characteristics of thetrans,trans,trans-[Co(hbg) 2] - model system is the solvent dependence of the optical spectra.

Original languageEnglish
Pages (from-to)4064-4069
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number21
Publication statusPublished - 2002

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Transferrin
Cobalt
Ligands
Anions
Transferrins
Ions
Oxygen
Radiation counters
Amines
Cations
Hydrogen
Nitrogen
Crystal structure
Single crystals
Spectroscopy
Derivatives
X rays
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Complexes of cobalt(III) with phenolate-containing polydentate ligands and bovine serum apo-transferrin : Towards creating spectroscopic models for cobalt(III)-tyrosinate interactions. / Shongwe, Musa S.; Al-Hatmi, Said K M; Marques, Helder M.; Smith, Rachel; Nukada, Ryoji; Mikuriya, Masahiro.

In: Journal of the Chemical Society, Dalton Transactions, No. 21, 2002, p. 4064-4069.

Research output: Contribution to journalArticle

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title = "Complexes of cobalt(III) with phenolate-containing polydentate ligands and bovine serum apo-transferrin: Towards creating spectroscopic models for cobalt(III)-tyrosinate interactions",
abstract = "Reaction of each member of a series of variously substituted N-(2-hydroxybenzyl)glycinate (hbg 2-) ligands [5-bromo- (5-Br-hbg 2-); 5-chloro- (5-Cl-hbg 2-); 3,5-dichloro- (3,5-Cl 2-hbg 2-); 5-chloro-3-methyl- (5,3-Cl,Me-hbg 2-); and 3,5-dimethyl- (3,5-Me 2-hbg 2-)] with cobalt(II) in stoichiometric amounts under ambient conditions afforded the Co III complex anions of the general formulatrans,trans,trans-[Co(hbg) 2] -. Single-crystal X-ray analyses of [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Cl 2-hbg) 2]3 and [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Me 2-hbg) 2]5 {[C 5H 10- NH 2] piperidinium counter ion} have revealed similar structural motifs of these compounds. Each of the crystal structures shows two non-equivalent complex anions in the unit cell connected through hydrogen bondingvia the piperidinium cation. The two hbg 2- ligands in each complex ion are arranged facially around the cobalt(III) ion and each ligand employs a phenolate oxygen, an amine nitrogen and a carboxylate oxygen to form a distorted octahedral geometry with C i symmetry. These compounds (1-5) serve as spectroscopic models for the interaction of cobalt(III) with tyrosinate ligands. The electronic spectrum of the compound [C 5H 10NH 2]-trans,trans,trans-[Co(5,3-Cl, Me-hbg) 2]4 bears a striking resemblance to that of the complex of cobalt(III) with bovine serum transferrin, [Co 2BTf]. In contrast to previous studies on the spectroscopy of the transferrins, one of the two ligand-field transitions expected to occur in [Co 2BTf] is evident in the electronic spectrum of this derivative of bovine serum transferrin in vitro. One of the fascinating characteristics of thetrans,trans,trans-[Co(hbg) 2] - model system is the solvent dependence of the optical spectra.",
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T1 - Complexes of cobalt(III) with phenolate-containing polydentate ligands and bovine serum apo-transferrin

T2 - Towards creating spectroscopic models for cobalt(III)-tyrosinate interactions

AU - Shongwe, Musa S.

AU - Al-Hatmi, Said K M

AU - Marques, Helder M.

AU - Smith, Rachel

AU - Nukada, Ryoji

AU - Mikuriya, Masahiro

PY - 2002

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N2 - Reaction of each member of a series of variously substituted N-(2-hydroxybenzyl)glycinate (hbg 2-) ligands [5-bromo- (5-Br-hbg 2-); 5-chloro- (5-Cl-hbg 2-); 3,5-dichloro- (3,5-Cl 2-hbg 2-); 5-chloro-3-methyl- (5,3-Cl,Me-hbg 2-); and 3,5-dimethyl- (3,5-Me 2-hbg 2-)] with cobalt(II) in stoichiometric amounts under ambient conditions afforded the Co III complex anions of the general formulatrans,trans,trans-[Co(hbg) 2] -. Single-crystal X-ray analyses of [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Cl 2-hbg) 2]3 and [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Me 2-hbg) 2]5 {[C 5H 10- NH 2] piperidinium counter ion} have revealed similar structural motifs of these compounds. Each of the crystal structures shows two non-equivalent complex anions in the unit cell connected through hydrogen bondingvia the piperidinium cation. The two hbg 2- ligands in each complex ion are arranged facially around the cobalt(III) ion and each ligand employs a phenolate oxygen, an amine nitrogen and a carboxylate oxygen to form a distorted octahedral geometry with C i symmetry. These compounds (1-5) serve as spectroscopic models for the interaction of cobalt(III) with tyrosinate ligands. The electronic spectrum of the compound [C 5H 10NH 2]-trans,trans,trans-[Co(5,3-Cl, Me-hbg) 2]4 bears a striking resemblance to that of the complex of cobalt(III) with bovine serum transferrin, [Co 2BTf]. In contrast to previous studies on the spectroscopy of the transferrins, one of the two ligand-field transitions expected to occur in [Co 2BTf] is evident in the electronic spectrum of this derivative of bovine serum transferrin in vitro. One of the fascinating characteristics of thetrans,trans,trans-[Co(hbg) 2] - model system is the solvent dependence of the optical spectra.

AB - Reaction of each member of a series of variously substituted N-(2-hydroxybenzyl)glycinate (hbg 2-) ligands [5-bromo- (5-Br-hbg 2-); 5-chloro- (5-Cl-hbg 2-); 3,5-dichloro- (3,5-Cl 2-hbg 2-); 5-chloro-3-methyl- (5,3-Cl,Me-hbg 2-); and 3,5-dimethyl- (3,5-Me 2-hbg 2-)] with cobalt(II) in stoichiometric amounts under ambient conditions afforded the Co III complex anions of the general formulatrans,trans,trans-[Co(hbg) 2] -. Single-crystal X-ray analyses of [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Cl 2-hbg) 2]3 and [C 5H 10NH 2]-trans,trans,trans-[Co(3,5-Me 2-hbg) 2]5 {[C 5H 10- NH 2] piperidinium counter ion} have revealed similar structural motifs of these compounds. Each of the crystal structures shows two non-equivalent complex anions in the unit cell connected through hydrogen bondingvia the piperidinium cation. The two hbg 2- ligands in each complex ion are arranged facially around the cobalt(III) ion and each ligand employs a phenolate oxygen, an amine nitrogen and a carboxylate oxygen to form a distorted octahedral geometry with C i symmetry. These compounds (1-5) serve as spectroscopic models for the interaction of cobalt(III) with tyrosinate ligands. The electronic spectrum of the compound [C 5H 10NH 2]-trans,trans,trans-[Co(5,3-Cl, Me-hbg) 2]4 bears a striking resemblance to that of the complex of cobalt(III) with bovine serum transferrin, [Co 2BTf]. In contrast to previous studies on the spectroscopy of the transferrins, one of the two ligand-field transitions expected to occur in [Co 2BTf] is evident in the electronic spectrum of this derivative of bovine serum transferrin in vitro. One of the fascinating characteristics of thetrans,trans,trans-[Co(hbg) 2] - model system is the solvent dependence of the optical spectra.

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