Comparison of two Mn(IV)Mn(IV)-bis-μ-oxo complexes {[Mn(IV)(N(4)(6-Me-DPEN))](2)(μ-O)(2)}(2+) and {[Mn(IV)(N(4)(6-Me-DPPN))](2)(μ-O)(2)}(2+)

The addition of tert-butyl hydro­peroxide ((t)BuOOH) to two structurally related Mn(II) complexes containing N,N-bis­(6-methyl-2-pyridyl­meth­yl)ethane-1,2-di­amine (6-Me-DPEN) and N,N-bis­(6-methyl-2-pyridyl­meth­yl)propane-1,2-di­amine (6-Me-DPPN) results in the formation of high-valent bis-oxo complexes, namely di-μ-oxido-bis­{[N,N-bis­(6-methyl-2-pyridylmeth­yl)ethane-1,2-di­amine]­manganese(II)}(Mn—Mn) bis­(tetra­phenyl­borate) dihydrate, [Mn(C(16)H(22)N(4))(2)O(2)](C(24)H(20)B)(2)·2H(2)O or {[Mn(IV)(N(4)(6-Me-DPEN))](2)(μ-O)(2)}(2BPh(4))(2H(2)O) (1) and di-μ-oxido-bis­{[N,N-bis­(6-methyl-2-pyridylmeth­yl)propane-1,3-di­amine]­manganese(II)}(Mn—Mn) bis­(tetra­phenyl­borate) diethyl ether disolvate, [Mn(C(17)H(24)N(4))(2)O(2)](C(24)H(20)B)(2)·2C(4)H(10)O or {[Mn(IV)(N(4)(6-MeDPPN))](2)(μ-O)(2)}(2BPh(4))(2Et(2)O) (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 Mn(IV) oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are consistent with the local pseudo-octa­hedral geometry.