Theoretical Perspectives on Redox "Non‐Innocent" Oxazolidine N‐Oxide Iron Nitroxide Complexes. Issue 5 (18th January 2013)

• Record Type: Journal Article
• Authors: Tewary, Subrata; Gass, Ian A.; Murray, Keith S.; Rajaraman, Gopalan
• Other Names: Murray Keith S. sponsoringEditor.; Oshio Hiroki sponsoringEditor.; Real Jose Antonio sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 5/6(2013)
• Page Start: 1024
• Page End: 1032
• Publication Date: 2013-01-18
• Subjects: Radicals -- Iron -- Density functional calculations -- Spin crossover -- Magnetic properties; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201201077
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: One‐electron redox processes in ligands that exhibit non‐innocent behaviour invariably leads to the generation of radical species, which, when coupled with redox‐active metal centres, can lead to strong magnetic exchange, ambiguous electronic structures and even spin crossover (SCO). We have chosen two iron complexes [Fe II (L · )2 ](BF4 )2 (1 ) and [Fe III (L – )2 ](BPh4 ) (2 ) [withL · = 4‐dimethyl‐2, 2‐di(2‐pyridyl)oxazolidine N ‐oxide] as the basis for an extensive theoretical study to determine the influence and interplay of the strong magnetic exchange, the redox non‐innocent behaviour and any possible spin transitions. A series of calculations established the low‐spin character of the Fe in both the complexes and gave us valuable insight into the electronic structure of1 and2 along with their one‐ and two‐electron reduced species. An attempt has been made to relate the bonding features to the energy difference between different spin states and to the influence of the exchange coupling on any possible SCO properties. Abstract : In this report we probe the innocent/non‐innocent nature of two radical metal complexes [Fe II (L · )2 ](BF4 )2 and [Fe III (L – )2 ](BPh4 ) [withL · = 4‐dimethyl‐2, 2‐di(2‐pyridyl)oxazolidine N ‐oxide] by using an extensive theoretical study.