The syntheses and characterisation of isostructural neptunium(iv) and plutonium(iv) complexes [An(IV)(TREN(TIPS))(Cl)] [An = Np, Pu; TREN(TIPS) = {N(CH2CH2NSiPr(i)3)3}(3-)] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(iii) and plutonium(iii) products [An(III)(TREN(TIPS))]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(iv) molecule is the first structurally characterised neptunium(iv)-amide complex.
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