Low-valent α-diimine iron complexes for catalytic olefin hydrogenation

Suzanne C. Bart, Eric J. Hawrelak, Emil Lobkovsky, Paul J. Chirik

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134 Scopus citations

Abstract

A family of low-valent α-diimine iron complexes has been synthesized and their utility in catalytic olefin hydrogenation reactions evaluated. Reduction of the ferrous dichloride complex [ArN=C(Me)C(Me)=NAr]FeCl 2 (Ar = 2,6-(CHMe 2) 2-C 6H 3) with sodium amalgam in benzene or toluene furnished the iron arene complexes, [ArN=C(Me)C(Me)=NAr]Fe(η 6-C 6H 5R) (R = H, Me). The solid-state structure of the toluene adduct revealed a contracted carbon-carbon backbone, short iron-imine bonds, and elongated imine nitrogen-carbon distances, suggesting significant reduction of the α-diimine ligand. The analogous reduction in alkane solvents afforded the bis(α-diimine) complex [ArN=C(Me)C(Me)=NAr] 2Fe, which has also been crystallographically characterized. The arene complexes and the bis(a-diimine) complexes are inactive for catalytic olefin hydrogenation. Performing the reduction in the presence of internal alkynes such as diphenylacetylene and bis(trimethylsilyl)acetylene furnished the alkyne adducts [ArN=C(Me)C(Me)=NAr]Fe(η 2-RC=CR) (R = Ph, SiMe 3 ). Analogous olefin complexes with 1,5-cyclooctadiene and cycloctene have also been isolated using similar reduction procedures. The olefin adducts provide more active precatalysts than the alkyne compounds for the hydrogenation of 1-hexene. In each case, formation of rfarene adducts serves as a major catalyst deactivation pathway.

Original languageEnglish (US)
Pages (from-to)5518-5527
Number of pages10
JournalOrganometallics
Volume24
Issue number23
DOIs
StatePublished - Nov 7 2005
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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