Mikael A Minier1, Stephen J Lippard. 1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. lippard@mit.edu.
Abstract
A series of asymmetrically carboxylate-bridged diiron(ii) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar(4F-Ph)CO2)2] (10), [Fe2(F2PIM)(Ar(Tol)CO2)2] (11), and [Fe2(F2PIM)(Ar(4F-Ph)CO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT (19)F NMR spectroscopy. These complexes are part of a rare family of syn N-donor diiron(ii) compounds, [Fe2(X2PIM)(RCO2)2], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOHred). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases.
A series of asymmetrically class="Chemical">carboxylate-bridged n class="Chemical">diiron(ii) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar(4F-Ph)CO2)2] (10), [Fe2(F2PIM)(Ar(Tol)CO2)2] (11), and [Fe2(F2PIM)(Ar(4F-Ph)CO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT (19)F NMR spectroscopy. These complexes are part of a rare family of syn N-donordiiron(ii) compounds, [Fe2(X2PIM)(RCO2)2], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOHred). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases.
Authors: Deanne Jackson Rudd; Matthew H Sazinsky; Stephen J Lippard; Britt Hedman; Keith O Hodgson Journal: Inorg Chem Date: 2005-06-27 Impact factor: 5.165
Authors: Maarten Merkx; Daniel A. Kopp; Matthew H. Sazinsky; Jessica L. Blazyk; Jens Müller; Stephen J. Lippard Journal: Angew Chem Int Ed Engl Date: 2001-08-03 Impact factor: 15.336
Authors: Natasa Mitić; Jennifer K Schwartz; Brian J Brazeau; John D Lipscomb; Edward I Solomon Journal: Biochemistry Date: 2008-07-16 Impact factor: 3.162