title: Covalent Metal-Metal-Bonded Mn4Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature-Independent Diamagnetism.
abstract: The electronic structures of the manganese(IV) cubane cluster Mn(μ3-NtBu)4(NtBu)4(1) and its one-electron-oxidized analogue, the 3:1 MnIV/MnVcluster [Mn(μ3-NtBu)4(NtBu)4]+[PF6]-(1+[PF6]), are described. The S = 0 spin quantum number of 1 is explained by a diamagnetic electronic structure where all metal-based d electrons are paired in Mn-Mn bonding orbitals. Temperature- and power-dependent studies of the S =1/2electron paramagnetic resonance signal of 1+are consistent with an electronic structure described as a delocalized one-electron radical.
authors.affiliation: Department of Chemistry, Temple University , 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
authors.forename: Shivaiah
authors.initials: S
authors.lastname: Vaddypally
authors.affiliation: Department of Chemistry, Temple University , 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Jovinelli
authors.affiliation: Department of Chemistry, Temple University , 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
authors.forename: Ian G
authors.initials: IG
authors.lastname: McKendry
authors.affiliation: Department of Chemistry, Temple University , 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
authors.forename: Michael J
authors.identifier: http://orcid.org/0000-0003-0212-2557
authors.initials: MJ
authors.lastname: Zdilla