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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.
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