Synthesis, characterization and solid state molecular structures of five- and six-coordinate primary amide manganese porphyrin complexes. (8th May 2017)

• Record Type: Journal Article
• Authors: Xu, Nan; Bevak, Alexander W.; Armstrong, Bernadette R.; Powell, Douglas R.
• Is Part Of: Polyhedron. Volume 127(2017)
• Page Start: 432
• Page End: 437
• Publication Date: 2017-05-08
• Subjects: Acrylamide -- Acetamide -- Porphyrin -- Manganese -- Primary amide; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.10.022
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: The reactions of the [(por)Mn(THF)2 ]ClO4 and [(OEP)Mn]ClO4 precursors with excess acrylamide or acetamide result in the formation of a series of five- and six-coordinate primary amide manganese porphyrin complexes. Two six-coordinate [(por)Mn(OC(NH2 )CHCH2 )2 ]ClO4 and one five-coordinate [(OEP)Mn(OC(NH2 )CH3 )]ClO4 complexes have been structurally characterized by X-ray crystallography. A sole O binding mode of the primary amide ligands in the complexes has been determined. Abstract: We report the synthesis and characterization of a number of primary amide manganese porphyrins from the reactions of the cationic [(por)Mn(THF)2 ]ClO4 (por = tetraphenylporphyrin dianion (TPP), tetra(p-chlorophenyl) porphyrin dianion (T(p-Cl)PP) and [(OEP)Mn]ClO4 (OEP = octaethylporphyrin dianion) precursors with excess acrylamide or acetamide. Two six-coordinate [(por)Mn(OC(NH2 )CHCH2 )2 ]ClO4 (por = TPP (1 ) T(p-Cl)PP (2 )) complexes and one five-coordinate [(OEP)Mn(OC(NH2 )CH3 )]ClO4 (4 ) complex have been structurally characterized by X-ray crystallography. A sole O binding mode of the primary amide ligands in these complexes has been determined. The redox behavior of the [(por)Mn(OC(NH2 )CHCH2 )2 ]ClO4 complexes has been studied by cyclic voltammetry, showing well-defined reversible reduction couples for both complexes.