Iron-Catalyzed Dehydrocoupling/Dehydrogenation of Amine-Boranes

James R. Vance, Andre Schaefer, Alasdair P. M. Robertson, Kajin Lee, Josh R Turner, George R. Whittell, Ian Manners*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

83 Citations (Scopus)

Abstract

The readily available iron carbonyl complexes, [CpFe(CO)(2)](2) (1) and CpFe(CO)(2)I (2) (Cp = eta-C5H5), were found to be efficient precatalysts for the dehydrocoupling/ dehydrogenation of the amine-borane Me2NH center dot BH3 (3) to afford the cyclodiborazane [Me2N-BH2](2) (4), upon UV photoirradiation at ambient temperature. In situ analysis of the reaction mixtures by B-11 NMR spectroscopy indicated that different two-step mechanisms operate in each case. Thus, precatalyst 1 dehydrocoupled 3 via the aminoborane Me2N=BH2 (5) which then cyclodimerized to give 4 via an off-metal process. In contrast, the reaction with precatalyst 2 proceeded via Me2NH-BH2-NMe2-BH3 (6) as the key intermediate, affording 4 as the final product after a second metal-mediated step. The related complex Cp2Fe2(CO)(3)(MeCN) (7), formed by photoirradiation of 1 in MeCN, was found to be a substantially more active dehydrocoupling catalyst and not to require photoactivation, but otherwise operated via a two-step mechanism analogous to that for 1. Significantly, detailed mechanistic studies indicated that the active catalyst generated from precatalyst 7 was heterogeneous in nature and consisted, of small iron nanoparticles (

Original languageEnglish
Pages (from-to)3048-3064
Number of pages17
JournalJournal of the American Chemical Society
Volume136
Issue number8
DOIs
Publication statusPublished - 26 Feb 2014

Keywords

  • CHEMICAL HYDROGEN STORAGE
  • PHOTOCHEMICAL SUBSTITUTION-REACTIONS
  • MOLECULAR-WEIGHT POLYAMINOBORANES
  • MAGNESIUM AMIDOBORANE COMPLEXES
  • OLEFIN-METATHESIS CATALYSTS
  • CROSS-COUPLING REACTIONS
  • BORON-NITROGEN BONDS
  • METAL-METAL BONDS
  • AMMONIA-BORANE
  • TRANSITION-METAL

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