title: Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.
abstract: Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.
authors.affiliation: †Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.
authors.forename: John
authors.initials: J
authors.lastname: McCracken
authors.affiliation: ‡Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.|§Department of Chemistry and Biochemistry, University of Massachusetts at Dartmouth, North Dartmouth, Massachusetts 02347, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Cappillino
authors.affiliation: ‡Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
authors.forename: Joshua S
authors.initials: JS
authors.lastname: McNally
authors.affiliation: †Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Krzyaniak
authors.affiliation: †Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Howart
authors.affiliation: ‡Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
authors.forename: Paul C
authors.initials: PC
authors.lastname: Tarves
authors.affiliation: ‡Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
authors.forename: John P
authors.initials: JP
authors.lastname: Caradonna
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D009589:Nitrogen Oxides / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D009589:Nitrogen Oxides; D014867:Water; D007501:Iron; C087991:nitrosyl chloride