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RESEARCH ARTICLE
Contents Vol 67(7)

Low-valent Iron Complexes Stabilised by a Bulky Guanidinate Ligand: Synthesis and Reactivity Studies*

Lea Fohlmeister A and Cameron Jones A B
+ Author Affiliations
- Author Affiliations

A School of Chemistry, PO Box 23, Monash University, Melbourne, Vic. 3800, Australia.

B Corresponding author. Email: cameron.jones@monash.edu

Australian Journal of Chemistry 67(7) 1011-1016 https://doi.org/10.1071/CH14157
Submitted: 17 March 2014  Accepted: 9 April 2014   Published: 29 May 2014

Abstract

A toluene-capped guanidinato iron(i) complex [(Pipiso)Fe(η6-toluene)] (Pipiso = [(DipN)2C(cis-NC5H8Me2-2,6)]–) was prepared by magnesium metal reduction of {[(Pipiso)FeII(µ-Br)]2} in toluene. The reactivity of the closely related FeI–FeI multiply bonded species, {[Fe(μ-Pipiso)]2} towards a range of unsaturated small molecule substrates was investigated, and found to be broadly similar to that of low-valent β-diketiminato iron complexes. That is, its reaction with CO yielded the iron(i) carbonyl complex [(Pipiso)Fe(CO)3], whereas reaction with CO2 formed the same product via an apparent reductive disproportionation of the substrate. In contrast, reaction between {[Fe(μ-Pipiso)]2} and CS2 led to reductive C=S bond cleavage and the isolation of {[(Pipiso)Fe]2(μ-S)(μ-CS)}. Different reactivity was seen with AdN3 (Ad = 1-adamantyl), which was reductively coupled by the iron(i) dimer to give iron(ii) hexaazenyl complex {[(Pipiso)Fe]2(μ-AdN6Ad)}.


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