title: Catalysis and Mechanism of H2 Release from Amine-Boranes by Diiron Complexes.
abstract: Studies focused on the dehydrogenation of amine-borane by diiron complexes that serve as well-characterized rudimentary models of the diiron subsite in [FeFe]-hydrogenase are reported. Complexes of formulation (μ-SCH2XCH2S)[Fe(CO)3]2, with X = CH2, CMe2, CEt2, NMe, NtBu, and NPh, 1-CO through 6-CO, respectively, were determined to be photocatalysts for release of H2 gas from a solution of H3B ← NHMe2 (B:A(s)), dissolved in THF. The thermal displacement of the tertiary amine-borane, H3B ← NEt3 (B:A(t)) from photochemically generated (μ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(μ-H)(BH2-NEt3)], 1-B:A(t) through 6-B:A(t), by P(OEt)3 was monitored by time-resolved FTIR spectroscopy. Rates and activation barriers for this substitution reaction were consistent with a dissociative mechanism for the alkylated bridgehead species 2-CO through 6-CO, and associative or interchange for 1-CO. DFT calculations supported an intermediate [I] for the dissociative process featuring a coordinatively unsaturated diiron complex stabilized by an agostic interaction between the metal center and the C-H bond of an alkyl group on the central bridgehead atom of the SRS linker. The rate of H2 production from the initially formed 1-B:A(s) through 6-B:A(s) complexes was inversely correlated with the lifetime of the analogous 1-B:A(t) through 6-B:A(t) adducts. Possible mechanisms are presented which feature involvement of the pendent nitrogen base as well as a separate mechanism for the all carbon bridgeheads.
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Allen M
authors.initials: AM
authors.lastname: Lunsford
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Jan H
authors.initials: JH
authors.lastname: Blank
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Salvador
authors.initials: S
authors.lastname: Moncho
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Steven C
authors.initials: SC
authors.lastname: Haas
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Sohail
authors.initials: S
authors.lastname: Muhammad
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Edward N
authors.initials: EN
authors.lastname: Brothers
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Marcetta Y
authors.initials: MY
authors.lastname: Darensbourg
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Ashfaq A
authors.initials: AA
authors.lastname: Bengali