Redox Isomerism in Main‐Group Chemistry: Tin Complex with o‐Iminoquinone Ligands. Issue 9 (2nd March 2018)

• Record Type: Journal Article
• Authors: Chegerev, Maxim G.; Piskunov, Alexandr V.; Starikova, Alyona A.; Kubrin, Stanislav P.; Fukin, Georgy K.; Cherkasov, Vladimir K.; Abakumov, Gleb A.
• Is Part Of: European journal of inorganic chemistry. Issue 9(2018)
• Page Start: 1087
• Page End: 1092
• Publication Date: 2018-03-02
• Subjects: Redox chemistry -- Isomers -- Redox‐active ligand -- Tin -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701361
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The bis‐chelate tin complex1, based on the 4, 6‐di‐ tert ‐butyl‐ N ‐( tert ‐butyl)‐ ortho ‐aminophenol ligand and representing the first example of a redox‐isomeric compound in main‐group chemistry, is synthesized and characterized by X‐ray diffraction analysis. Complex1 exists in two electromeric forms in nonpolar solvents: a diamagnetic pseudotetrahedral (AP)2 Sn IV (1a ) and a paramagnetic tetragonal‐pyramidal structure of low‐valence tin (imSQ)2 Sn II (1b ) (where AP and imSQ are the dianionic and radical‐anionic forms of the ligand, respectively). The reversible redox‐isomeric rearrangement between1a and1b is investigated in solution by means of magnetochemistry, EPR spectroscopy, UV/Vis spectroscopy, and 119 Sn Mössbauer spectroscopy. This interconversion can be quenched by an addition of a strong donor ligand, such as pyridine (Py), resulting in an octahedral complex (AP)2 Sn IV (Py)2 (2 ) that does not undergo redox isomerism. Abstract : A bis‐chelate tin complex bearing a redox‐active o ‐aminophenol ligand, representing the first example of a redox‐isomeric compound in main‐group chemistry, is synthesized and investigated. This complex exists in nonpolar solvents as an equilibrium mixture of two different isomers: a diamagnetic pseudotetrahedral tin(IV) compound and a paramagnetic tetragonal‐pyramidal tin(II) structure.