Oxygen‐Atom Transfer Chemistry and Thermolytic Properties of a Di‐<i>tert</i>‐Butylphosphate‐Ligated Mn₄O₄ Cubane

Abstract [Mn 4 O 4 {O 2 P(O t Bu) 2 } 6 ] ( 1 ), an Mn 4 O 4 cubane complex combining the structural inspiration of the photosystem II oxygen‐evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen‐atom acceptor (PEt 3 ), to give the butterfly complex [Mn 4 O 2 {O 2 P(O t Bu) 2 } 6 (OPEt 3 ) 2 ]. The cubane structure is restored by reaction of the latter complex with the O‐atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X‐ray absorption spectroscopy to determine the fate of the Mn 4 O 4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn II species. Finally, the related butterfly complex [Mn 4 O 2 {O 2 P(pin)} 6 (bpy) 2 ] (pin=pinacolate) is described.