TY - JOUR
T1 - Heme/non-heme diiron(II) complexes and O2, CO, and NO adducts as reduced and substrate-bound models for the active site of bacterial nitric oxide reductase
AU - Wasser, Ian M.
AU - Huang, Hong Wei
AU - Moënne-Loccoz, Pierre
AU - Karlin, Kenneth D.
PY - 2005/3/16
Y1 - 2005/3/16
N2 - As a first generation model for the reactive reduced active-site form of bacterial nitric oxide reductase, a heme/non-heme diiron(II) complex [( 6L)FeII-FeII-(CI)]+ (2) {where 6L = partially fluorinated tetraphenylporphyrin with a tethered tetradentate TMPA chelate; TMPA = tris(2-pyridyl)amine} was generated by reduction of the corresponding μ-oxo diferric compound [(6L) FeIII-O-FeIII-CI]+ (1). Coordination chemistry models for reactions of reduced NOR with O2, CO, and NO were also developed. With O2 and CO, adducts are formed, [(6L) FeIII(O2-)(thf)⋯FeII-Cl] B(C6F5)4 (2a·O2) {λmax 418 (Soret), 536 nm; νO-O = 1176 cm -1, νFe-O = 574 cm-1 and [( 6L)FeII(CO)(thf)FeII-Cl]B(C6F 5)4 (2a·CO) {νCO 1969 cm -1}, respectively. Reaction of purified nitric oxide with 2 leads to the dinitrosyl complex [(6L)Fe(NO)Fe(NO)-Cl]B(C6F 5)4 (2a·(NO)2) with νNO absorptions at 1798 cm-1 (non-heme Fe-NO) and 1689 cm-1 (heme-NO).
AB - As a first generation model for the reactive reduced active-site form of bacterial nitric oxide reductase, a heme/non-heme diiron(II) complex [( 6L)FeII-FeII-(CI)]+ (2) {where 6L = partially fluorinated tetraphenylporphyrin with a tethered tetradentate TMPA chelate; TMPA = tris(2-pyridyl)amine} was generated by reduction of the corresponding μ-oxo diferric compound [(6L) FeIII-O-FeIII-CI]+ (1). Coordination chemistry models for reactions of reduced NOR with O2, CO, and NO were also developed. With O2 and CO, adducts are formed, [(6L) FeIII(O2-)(thf)⋯FeII-Cl] B(C6F5)4 (2a·O2) {λmax 418 (Soret), 536 nm; νO-O = 1176 cm -1, νFe-O = 574 cm-1 and [( 6L)FeII(CO)(thf)FeII-Cl]B(C6F 5)4 (2a·CO) {νCO 1969 cm -1}, respectively. Reaction of purified nitric oxide with 2 leads to the dinitrosyl complex [(6L)Fe(NO)Fe(NO)-Cl]B(C6F 5)4 (2a·(NO)2) with νNO absorptions at 1798 cm-1 (non-heme Fe-NO) and 1689 cm-1 (heme-NO).
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U2 - 10.1021/ja0458773
DO - 10.1021/ja0458773
M3 - Article
C2 - 15755147
AN - SCOPUS:14944339704
SN - 0002-7863
VL - 127
SP - 3310
EP - 3320
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 10
ER -