Comparison of two MnMn-bis-μ-oxo complexes {[Mn(N(6-Me-DPEN))](μ-O)} and {[Mn(N(6-Me-DPPN))](μ-O)}.

The addition of -butyl hydro-peroxide ( BuOOH) to two structurally related Mn complexes containing -bis-(6-methyl-2-pyridyl-meth-yl)ethane-1,2-di-amine (6-Me-DPEN) and -bis-(6-methyl-2-pyridyl-meth-yl)propane-1,2-di-amine (6-Me-DPPN) results in the formation of high-valent bis-oxo complexes, namely di-μ-oxido-bis-{[,-bis-(6-methyl-2-pyridylmeth-yl)ethane-1,2-di-amine]-manganese(II)}(-) bis-(tetra-phenyl-borate) dihydrate, [Mn(CHN)O](CHB)·2HO or {[Mn(N(6-Me-DPEN))](-O)}(2BPh)(2HO) () and di-μ-oxido-bis-{[,-bis-(6-methyl-2-pyridylmeth-yl)propane-1,3-di-amine]-manganese(II)}(-) bis-(tetra-phenyl-borate) diethyl ether disolvate, [Mn(CHN)O](CHB)·2CHO or {[Mn(N(6-MeDPPN))](-O)}(2BPh)(2EtO) (). Complexes and both contain the 'diamond core' motif found previously in a number of iron, copper, and manganese high-valent bis-oxo compounds. The flexibility in the propyl linker in the ligand scaffold of , as compared to that of the ethyl linker in , results in more elongated Mn-N bonds, as one would expect. The Mn-Mn distances and Mn-O bond lengths support an Mn oxidation state assignment for the Mn ions in both and . The angles around the Mn centers are consistent with the local pseudo-octa-hedral geometry.