Inorganic Chemistry, Vol.56, No.7, 3733-3737, 2017
Covalent Metal Metal-Bonded Mn-4 Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature -Independent Diamagnetism
The electronic structures of the manganese (IV) cubane cluster Mn(mu(3)-(NBu)-Bu-t)(4)((NBu)-Bu-t)(4) (1) and its one-electron-oxidized analogue the 3:1 Mn-IV/Mn-V cluster [Mn(mu(3)-(NBu)-Bu-t)(4)((NBu)-Bu-t)(4)](+) [PF6](-) (1(+) [PF6]) are described. The S = 0 spin quantum number of 1 is explained by a diamagnetic electronic structure where all metal-liased delectrons are paired in Mn-Mn bonding orbitals. Temperature-and power-dependent studies of the S =1/2 electron paramagnetic resonance signal of 1(+) are consistent with an electronic structure described as adelocalized one-electron radical.