Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety

[Rh III H{( t Bu 2 PCH 2 SiMe 2 NSiMe 2 CH 2 P t Bu{CMe 2 CH 2 })}], ([RhH(PNP*)]), reacts with O 2 in the time taken to mix the reagents to form a 1:1 η 2 ‐O 2 adduct, for which OO bond length is discussed with reference to the reducing power of [RhH(PNP*)]; DFT calculations faithfully replicate the observed O–O distance, and are used to understand the oxidation state of this coordinated O 2 . The reactivity of [Rh(O 2 )(PNP)] towards H 2 , CO, N 2 , and O 2 is tested and compared to the associated DFT reaction energies. Three different reagents effect single oxygen atom transfer to [RhH(PNP*)]. The resulting [RhO(PNP)], characterized at and above −60 °C and by DFT calculations, is a ground‐state triplet, is nonplanar, and reacts, above about +15 °C, with its own t Bu CH bond, to cleanly form a diamagnetic complex, [Rh(OH){N(SiMe 2 CH 2 P t Bu 2 )(SiMe 2 CH 2 P t Bu{CMe 2 CH 2 })}].