N2 Functionalization at Iron Metallaboratranes
- 18 October 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 133 (45), 18118-18121
- https://doi.org/10.1021/ja208675p
Abstract
The reactivity of the anionic dinitrogen complex [(TPB)Fe(N2)]− (TPB = tris[2-(diisopropylphosphino)phenyl]borane) toward silicon electrophiles has been examined. [(TPB)Fe(N2)]− reacts with trimethylsilyl chloride to yield the silyldiazenido complex (TPB)Fe(NNSiMe3), which is reduced by Na/Hg in THF to yield the corresponding sodium-bound anion [(TPB)Fe(NNSiMe3)]Na(THF). The use of 1,2-bis(chlorodimethylsilyl)ethane in the presence of excess Na/Hg results in the disilylation of the bound N2 molecule to yield the disilylhydrazido(2−) complex (TPB)Fe≡NR (R = 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl). One of the phosphine arms of TPB in (TPB)Fe≡NR can be substituted by CO or tBuNC to yield crystalline adducts (TPB)(L)Fe≡NR (L = CO, tBuNC). The N–N bond in (TPB)(tBuNC)Fe≡NR is cleaved upon standing at room temperature to yield a phosphoraniminato/disilylamido iron(II) complex. The flexibility of the Fe–B linkage is thought to play a key role in these transformations of Fe-bound dinitrogen.This publication has 39 references indexed in Scilit:
- Structure and bonding in three-coordinate N-heterocyclic carbene adducts of iron(ii) bis(trimethylsilyl)amideChemical Communications, 2011
- ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR)Coordination Chemistry Reviews, 2011
- Terminal Iron Dinitrogen and Iron Imide Complexes Supported by a Tris(phosphino)borane LigandAngewandte Chemie, 2011
- Triggering N2 uptake via redox-induced expulsion of coordinated NH3 and N2 silylation at trigonal bipyramidal ironNature Chemistry, 2010
- Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?Dalton Transactions, 2010
- Climbing Nitrogenase: Toward a Mechanism of Enzymatic Nitrogen FixationAccounts of Chemical Research, 2009
- Catalytic nitrene transfer from an imidoiron(iii) complex to form carbodiimides and isocyanatesChemical Communications, 2009
- On the feasibility of N 2 fixation via a single-site Fe I /Fe IV cycle: Spectroscopic studies of Fe I (N 2 )Fe I , Fe IV N, and related speciesProceedings of the National Academy of Sciences of the United States of America, 2006
- Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum CenterAccounts of Chemical Research, 2005
- Synthesis and Structure of a Trigonal Monopyramidal Fe(II) Complex and Its Paramagnetic Carbon Monoxide DerivativeJournal of the American Chemical Society, 1996