TY - JOUR
T1 - Structural and spectroscopic features of a cis (hydroxo)-FeIII-(carboxylato) configuration as an active site model for lipoxygenases
AU - Ogo, Seiji
AU - Yamahara, Ryo
AU - Roach, Mark
AU - Suenobu, Tomoyoshi
AU - Aki, Michihiko
AU - Ogura, Takashi
AU - Kitagawa, Teizo
AU - Masuda, Hideki
AU - Fukuzumi, Shunichi
AU - Watanabe, Yoshihito
PY - 2002/10/21
Y1 - 2002/10/21
N2 - In our preliminary communication (Ogo, S.; Wada, S.; Watanabe, Y.; Iwase, M.; Wada, A.; Harata, M.; Jitsukawa, K.; Masuda, H.; Einaga, H. Angew. Chem., Int. Ed. 1998, 37, 2102-2104), we reported the first example of X-ray analysis of a mononuclear six-coordinate (hydroxo)iron(III) non-heme complex, [FeIII(tnpa)(OH)(RCO2)]-CIO4 [tnpa = tris(6-neopentylamino-2-pyridylmethyl)amine; for 1, R = C6H5], which has a characteristic cis (hydroxo)-FeIII-(carboxylato) configuration that models the cis (hydroxo)-FeIII-(carboxylato) moiety of the proposed (hydroxo)- iron(III) species of lipoxygenases. In this full account, we report structural and spectroscopic characterization of the cis (hydroxo)-FeIII-(carboxylato) configuration by extending the model complexes from 1 to [FeIII(tnpa)(OH)(RCO2)]-CIO4 (2, R = CH3; 3, R = H) whose cis (hydroxo)-FeIII-(carboxylato) moieties are isotopically labeled by 18OH-, 16OD-, 18OD-, 12CH312 C18O2-, 12CH313C16 O2-, 13CH312C16 O2-, 13CH313C16 O2-, and H13C16O2-. Complexes 1-3 are characterized by X-ray analysis, IR, EPR, and UV-vis spectroscopy, and electrospray ionization mass spectrometry (ESI-MS).
AB - In our preliminary communication (Ogo, S.; Wada, S.; Watanabe, Y.; Iwase, M.; Wada, A.; Harata, M.; Jitsukawa, K.; Masuda, H.; Einaga, H. Angew. Chem., Int. Ed. 1998, 37, 2102-2104), we reported the first example of X-ray analysis of a mononuclear six-coordinate (hydroxo)iron(III) non-heme complex, [FeIII(tnpa)(OH)(RCO2)]-CIO4 [tnpa = tris(6-neopentylamino-2-pyridylmethyl)amine; for 1, R = C6H5], which has a characteristic cis (hydroxo)-FeIII-(carboxylato) configuration that models the cis (hydroxo)-FeIII-(carboxylato) moiety of the proposed (hydroxo)- iron(III) species of lipoxygenases. In this full account, we report structural and spectroscopic characterization of the cis (hydroxo)-FeIII-(carboxylato) configuration by extending the model complexes from 1 to [FeIII(tnpa)(OH)(RCO2)]-CIO4 (2, R = CH3; 3, R = H) whose cis (hydroxo)-FeIII-(carboxylato) moieties are isotopically labeled by 18OH-, 16OD-, 18OD-, 12CH312 C18O2-, 12CH313C16 O2-, 13CH312C16 O2-, 13CH313C16 O2-, and H13C16O2-. Complexes 1-3 are characterized by X-ray analysis, IR, EPR, and UV-vis spectroscopy, and electrospray ionization mass spectrometry (ESI-MS).
UR - http://www.scopus.com/inward/record.url?scp=0037152395&partnerID=8YFLogxK
U2 - 10.1021/ic0200040
DO - 10.1021/ic0200040
M3 - Article
C2 - 12377047
AN - SCOPUS:0037152395
SN - 0020-1669
VL - 41
SP - 5513
EP - 5520
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -