ic702154z_si_020.cif (38.24 kB)
Synthesis, Characterization, and Reactivity of Iron Trisamidoamine Complexes That Undergo Both Metal- and Ligand-Centered Oxidative Transformations
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posted on 2008-02-04, 00:00 authored by Remle Çelenligil-Çetin, Patrina Paraskevopoulou, Rupam Dinda, Richard J. Staples, Ekkehard Sinn, Nigam P. Rath, Pericles StavropoulosFunctional systems that combine redox-active metals and noninnocent ligands are no longer rare chemical oddities;
they are instead emerging as significant components of catalytic and enzymatic reactions. The present work examines
the synthetic and functional aspects of iron compounds ligated by a family of new trisamidoamine ligands of the
type [(RNC6H4)3N]3- (L1). When R is the electron-rich 4-t-Bu−Ph moiety, the ligand can undergo oxidative
rearrangement and store oxidizing equivalents under specific conditions. Starting ferrous complexes of the general
formula [(L1)FeIIsolv]- (solv = CH3CN, dimethylformamide) can be easily oxidized (a) by dioxygen to afford the
corresponding [(L1)FeIIIOH]- complexes, featuring several cases of terminal hydroxo units, and (b) by organochlorides
(R−Cl) to provide [(L1)FeIIIsolv] congeners and coupled R−R products. Efforts to synthesize [(L1)FeIII−O−FeIII(L1)]2-
by using [Cl3FeIII−O−FeIIICl3]2- indicate that intrinsic FeIIICl units can oxidatively rearrange the ligand to afford
[(L1re)(Cl)FeII][Et4N]2, although the oxidizing equivalent is not retained. Compound [(L1re)(Cl)FeII][Et4N]2 can be further
oxidized to [(L1re-2)(Cl)FeIII][Et4N] by CH2Cl2. Finally, oxidation of [(L1)FeIIIsolv] by FeCl3 affords [(L1reH)(Cl)FeII(μ-Cl)2FeII(Cl)(L1re-2H)], which features a similar ligand rearrangement that also gives rise to a diamagnetic, doubly
oxidized moiety. These results underscore the complexity of chemical transformations available to systems in which
both the metal and the ligand are redox-active entities.
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Fe III solvligand rearrangementFe II solvnoninnocent ligandsCH 3 CNL 1Iron Trisamidoamine Complexeschemical transformationsiron compounds ligatedtrisamidoamine ligands2 Fe IIRNCchemical odditiesFe III OHCH 2 Cl 2terminal hydroxo unitsferrous complexes3 Noxidative rearrangementFeCl 3oxidizing equivalentstore oxidizing equivalentsFe III Cl units
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