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

• Published in: Acta crystallographica. Section E, Crystallographic communications Vol. 76; no. Pt 7; pp. 1042 - 1046
• Main Authors: Coggins, Michael K, Downing, Alexandra N, Kaminsky, Werner, Kovacs, Julie A
• Format: Journal Article
• Language: English
• Published: England 01.07.2020
• Subjects: crystal structure; metal-oxo; high-valent; manganese; transition metal
• ISSN: 2056-9890; 2056-9890
• DOI: 10.1107/S2056989020004557

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(C H N ) O ](C H B) ·2H O or {[Mn (N (6-Me-DPEN))] ( -O) }(2BPh )(2H O) ( ) 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(C H N ) O ](C H B) ·2C H O or {[Mn (N (6-MeDPPN))] ( -O) }(2BPh )(2Et O) ( ). 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.