title: Formation of {[HIPTN(3)N]Mo(III)H}(-) by heterolytic cleavage of H(2) as established by EPR and ENDOR spectroscopy.
abstract: MoN(2) (Mo = [(HIPTNCH(2)CH(2))(3)N]Mo, where HIPT = 3,5-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(3)) is the first stage in the reduction of N(2) to NH(3) by Mo. Its reaction with dihydrogen in fluid solution yields "MoH(2)", a molybdenum-dihydrogen compound. In this report, we describe a comprehensive electron paramagnetic resonance (EPR) and (1/2)H/(14)N electron nuclear double resonance (ENDOR) study of the product of the reaction between MoN(2) and H(2) that is trapped in frozen solution, 1. EPR spectra of 1 show that it has a near-axial g tensor, g = [2.086, 1.961, 1.947], with dramatically reduced g anisotropy relative to MoN(2). Analysis of the g values reveal that this anion has the Mo(III), [d(xz), d(yz)](3) orbital configuration, as proposed for the parent MoN(2) complex, and that it undergoes a strong pseudo-Jahn-Teller (PJT) distortion. Simulations of the 2D 35 GHz (1)H ENDOR pattern comprised of spectra taken at multiple fields across the EPR envelope (2 K) show that 1 is the [MoH](-) anion. The 35 GHz Mims pulsed (2)H ENDOR spectra of 1 prepared with (2)H(2) show the corresponding (2)H(-) signal, with a substantial deuterium isotope effect in a(iso). Radiolytic reduction of a structural analogue, Mo(IV)H, at 77 K, confirms the assignment of 1. Analysis of the 2D (14)N ENDOR pattern for the ligand amine nitrogen further reveals the presence of a linear N(ax)-Mo-H(-) molecular axis that is parallel to the unique magnetic direction (g(1)). The ENDOR pattern of the three equatorial nitrogens is well-reproduced by a model in which the Mo-N(eq) plane has undergone a static, not dynamic, PJT distortion, leading to a range of hyperfine couplings for the three N(eq)'s. The finding of a nearly axial hyperfine coupling tensor for the terminal hydride bound Mo supports the earlier proposal that the two exchangeable hydrogenic species bound to the FeMo cofactor of the nitrogense turnover intermediate, which has accumulated four electrons/protons (E(4)), are hydrides that bridge two metal ions, not terminal hydrides.
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: R Adam
authors.initials: RA
authors.lastname: Kinney
authors.forename: Dennis G H
authors.initials: DG
authors.lastname: Hetterscheid
authors.forename: Brian S
authors.initials: BS
authors.lastname: Hanna
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
authors.forename: Brian M
authors.initials: BM
authors.lastname: Hoffman
mesh_terms: D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*
chemical_list: D006859:Hydrogen; D008982:Molybdenum; D009584:Nitrogen