Iron-Mediated Amination of Hydrocarbons in the Gas Phase

✍ Scribed by Mark Brönstrup; Ilona Kretzschmar; Detlef Schröder; Helmut Schwarz

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 223 KB
• Volume: 81
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/(sici)1522-2675(19981216)81:12<2348::aid-hlca2348>3.0.co;2-p

✦ Synopsis

Dedicated to Professor Werner Schroth on the occasion of his 70th birthday

FeNH is chosen as a model system to probe the transition-metal-mediated transfer of imine groups in the gas phase by mass-spectrometric means. Ab initio calculations at the MR-ACPF level predict FeNH to have a linear sextet ground state ( 6 S ); a bent quartet state ( 4 A') and a linear doublet state ( 2 D) are higher in energy by 0.14 eV and 0.51 eV, respectively. The bond-dissociation energy is determined to D(Fe ÀNH) 69 AE 2 kcal mol À1 using ion-molecule reactions. Charge-stripping experiments combined with ab initio calculations yield an ionization energy of IE( FeNH ) 15.7 AE 0.5 eV. The chemical behavior of FeNH towards oxygen, water, hydrogen, aliphatic hydrocarbons, benzene, and toluene reveals an intrinsically high reactivity of FeNH . Because a transfer of the hNHi fragment to the substrate is feasible in most cases, attractive amination reactions like methane 3 methylamine, benzene 3 aniline, or toluene 3 benzylidenamine can be afforded by FeNH .