Journal
INORGANIC CHEMISTRY
Volume 51, Issue 18, Pages 10043-10054Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic301704f
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Funding
- NIH [GM-070757, RR 027690]
- Gordon and Betty Moore Foundation
- NSF graduate fellowship
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This article describes the synthesis and characterization of several low-spin iron(II) complexes that coordinate hydrazine (N2H4), hydrazido (N2H3-), and ammonia. The sterically encumbered tris(di-meta-terphenylphosphino)borate ligand, [PhBP3mter](-), is introduced to provide access to species that cannot be stabilized with the [PhBP3Ph](-) ligand ([PhBP3R](-) = PhB(CH2PR2)(3)(-)). Treatment of [PhBP3mter]FeMe with hydrazine generates the unusual 5-coordinate hydrazido complex [PhBP3mter]Fe(eta(2)-N2H3) (1), in which the hydrazido serves as an L2X-type ligand. Upon coordination of an L-type ligand, the hydrazido shifts to an LX-type ligand, generating [PhBP3mter]Fe(L)(eta(2)-N2H3) (L = N2H4 (2) or NH3 (3)). In contrast, treatment of [PhBP3Ph]FeMe with hydrazine forms the adduct [PhBP3Ph]Fe(Me)(;eta(2)-N2H4) (5). Complex 5 is thermally unstable to methane loss, generating intermediate [PhBP3Ph]Fe(eta(2)-N2H3), which undergoes bimolecular coupling to produce {[PhBP3Ph]Fe}(2)(mu-eta(1):eta(1)-N2H4)(mu-eta(2):eta(2)-N2H2) The oxidation of these and related hydrazine and hydrazido species is also presented. For example, oxidation of 1 or 5 with Pb(OAc)(4) results in disproportionation of the N2Hx ligand (x = 3, 4), and formation of [PhBP3R]Fe(NH3)(OAc) (R = Ph (9) and mter (11)).
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