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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