Synthesis, characterization, electrochemical properties and theoretical calculations of (BIAN) iron complexes. (1st February 2019)

• Record Type: Journal Article
• Authors: Larson, Patrick J.; Wekesa, Francis S.; Singh, Arpita; Smith, Cecilia R.; Rajput, Amit; McGovern, Gregory P.; Unruh, Daniel K.; Cozzolino, Anthony F.; Findlater, Michael
• Is Part Of: Polyhedron. Volume 159(2019)
• Page Start: 365
• Page End: 374
• Publication Date: 2019-02-01
• Subjects: Iron -- BIAN -- Cyclic voltammetry -- X-ray crystallography -- Redox non-innocence; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2018.11.060
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A series of iron η 6 -arene complexes of general formula [(BIAN)Fe(arene)] have been prepared and characterized. The solid state structures of these complexes, combined with cyclic voltammetry and augmented by DFT calculations allowed us to more fully describe the electronic structure of the complexes and understand the effects of arene identity. Abstract: Reduction of the tetrahedral complex (BIAN)FeCl2 (6 ) (BIAN = 1, 2-bis[(2, 6-diisopropylphenyl)imino]acenaphthene) in the presence of an arene, either as reaction solvent or in pentane solution affords a series of (BIAN)Fe(η 6 -arene) complexes (10 –13 ). In the case of the sterically encumbered arene 2-methylnapthalene, 6 was converted to the (BIAN)Fe(COD) (14 ) (COD = 1, 5-cyclooctadiene) complex first, before subsequent hydrogenation in the presence of 2-methylnaphthalene afforded the desired arene complex (15 ). The electronic structure of the arene complexes was interrogated, and the question of ligand redox non-innocence was addressed using X-ray diffraction studies as well as DFT and cyclic voltammetry.