Comparison of two MnIVMnIV-bis-μ-oxo complexes {[MnIV(N4(6-Me-DPEN))]2(μ-O)2}2+ and {[MnIV(N4(6-Me-DPPN))]2(μ-O)2}2.

The addition of tert-butyl hydro-peroxide ( t BuOOH) to two structurally related MnII complexes containing N,N-bis-(6-methyl-2-pyridyl-meth-yl)ethane-1,2-di-amine (6-Me-DPEN) and N,N-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-{[N,N-bis-(6-methyl-2-pyridylmeth-yl)ethane-1,2-di-amine]-manganese(II)}(Mn-Mn) bis-(tetra-phenyl-borate) dihydrate, [Mn(C16H22N4)2O2](C24H20B)2·2H2O or {[MnIV(N4(6-Me-DPEN))]2(μ-O)2}(2BPh4)(2H2O) (1) and di-μ-oxido-bis-{[N,N-bis-(6-methyl-2-pyridylmeth-yl)propane-1,3-di-amine]-manganese(II)}(Mn-Mn) bis-(tetra-phenyl-borate) diethyl ether disolvate, [Mn(C17H24N4)2O2](C24H20B)2·2C4H10O or {[MnIV(N4(6-MeDPPN))]2(μ-O)2}(2BPh4)(2Et2O) (2). Complexes 1 and 2 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 2, as compared to that of the ethyl linker in 1, results in more elongated Mn-N bonds, as one would expect. The Mn-Mn distances and Mn-O bond lengths support an MnIV oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are consistent with the local pseudo-octa-hedral geometry.