Catalysis and Mechanism of H2 Release from Amine-Boranes by Diiron Complexes

Allen M. Lunsford, Jan H. Blank, Salvador Moncho Escriva, Steven C. Haas, Muhammad Sohail, Edward Brothers, Marcetta Y. Darensbourg, Ashfaq A. Bengali

Research output: Contribution to journalArticle

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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:As), dissolved in THF. The thermal displacement of the tertiary amine-borane, H3B ← NEt3 (B:At) from photochemically generated (μ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(μ-H)(BH2-NEt3)], 1-B:At through 6-B:At, 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:As through 6-B:As complexes was inversely correlated with the lifetime of the analogous 1-B:At through 6-B:At adducts. Possible mechanisms are presented which feature involvement of the pendent nitrogen base as well as a separate mechanism for the all carbon bridgeheads.

Original languageEnglish
Pages (from-to)964-973
Number of pages10
JournalInorganic Chemistry
Volume55
Issue number2
DOIs
Publication statusPublished - 19 Jan 2016

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Boranes
boranes
Carbon Monoxide
Catalysis
catalysis
Amines
amines
dehydrogenation
adducts
activation
substitutes
formulations
nitrogen
life (durability)
carbon
gases
Hydrogenase
metals
spectroscopy
atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Catalysis and Mechanism of H2 Release from Amine-Boranes by Diiron Complexes. / Lunsford, Allen M.; Blank, Jan H.; Moncho Escriva, Salvador; Haas, Steven C.; Sohail, Muhammad; Brothers, Edward; Darensbourg, Marcetta Y.; Bengali, Ashfaq A.

In: Inorganic Chemistry, Vol. 55, No. 2, 19.01.2016, p. 964-973.

Research output: Contribution to journalArticle

Lunsford, Allen M. ; Blank, Jan H. ; Moncho Escriva, Salvador ; Haas, Steven C. ; Sohail, Muhammad ; Brothers, Edward ; Darensbourg, Marcetta Y. ; Bengali, Ashfaq A. / Catalysis and Mechanism of H2 Release from Amine-Boranes by Diiron Complexes. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 2. pp. 964-973.
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