The Features of Interaction of Bis(4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐amidophenolato)tin(IV) with Bromine and Iodine

The oxidation of tin(IV) bis-amidophenolate (APiPr)2Sn·THF (I) by bromine and iodine leads to the formation of monoradical mixed-ligand complexes (APiPr)(ISQiPr)SnBr·THF (II) and (APiPr)(ISQiPr)SnI·THF (III) or diradical complexes (ISQiPr)2SnBr2 (IV) and (ISQiPr)2SnI2 (V), respectively [APiPr = dianion 4, 6-di-tert-butyl-N-(2, 6-diisopropylphenyl)-o-amidophenolate; ISQiPr = radical-anion 4, 6-di-tert-butyl-N-(2, 6-diisopropylphenyl)-o-iminobenzosemiquinone], depending on the molar ratio of reagents (2:1 or 1:1). According to EPR data for compounds II and III, the unpaired electron is delocalized between both organic ligands. The EPR spectrum of IV in toluene matrix at 130 K is typical for diradical species with S = 1 with parameters D = 530 G, E = 105 G. The mixed-ligand complexes II and III are unstable and undergo to symmetrization leading to formation of IV or V. The molecular structures of IV and V are determined by X-ray analysis.

[1]  E. V. Ilyakina,et al.  Mono- o -semiquinonato mixed-halogenato tin(IV) complexes: EPR spectroscopic and X-ray investigations , 2012 .

[2]  P. Chirik.  Preface: Forum on redox-active ligands. , 2011, Inorganic chemistry.

[3]  A. Piskunov,et al.  Zinc and cadmium complexes based on 3,6-di-tert-butyl-o-benzoquinone , 2011 .

[4]  A. Piskunov,et al.  New tin(iv) o-iminosemiquinone complexes , 2010 .

[5]  A. Piskunov,et al.  Zinc molecular complexes with sterically hindered o-quinone and o-iminoquinone , 2009 .

[6]  A. Poddel’sky,et al.  Transition metal complexes with bulky 4,6-di-tert-butyl-N-aryl(alkyl)-o-iminobenzoquinonato ligands: Structure, EPR and magnetism , 2009 .

[7]  A. Piskunov,et al.  Oxidation by oxygen and sulfur of Tin(IV) derivatives containing a redox-active o-amidophenolate ligand. , 2008, Chemistry.

[8]  A. Piskunov,et al.  Novel germanium(IV) catecholate complexes , 2008 .

[9]  O. Sato,et al.  Control of magnetic properties through external stimuli. , 2007, Angewandte Chemie.

[10]  A. Piskunov,et al.  New lead(II) catecholate and o-semiquinone complexes , 2006 .

[11]  A. Piskunov,et al.  New tin(II) and tin(IV) amidophenolate complexes , 2006 .

[12]  A. Piskunov,et al.  Free radical fixation by tin(IV) diphenylcatecholate complexes , 2006 .

[13]  A. Poddel’sky,et al.  Oxidative addition of 3,6-di-tert-butyl-o-benzoquinone and 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinone to SnCl2 , 2005 .

[14]  C. Pierpont.  Unique properties of transition metal quinone complexes of the MQ3 series , 2001 .

[15]  C. Pierpont.  Studies on charge distribution and valence tautomerism in transition metal complexes of catecholate and semiquinonate ligands , 2001 .

[16]  M. I. Kabachnik,et al.  Silicon-containing radicals and diradicals with 3,5-DI-tert-butylpyrocatechol ligands , 1981 .

[17]  V. Ershov,et al.  Radical-anion ion pairs with a six-coordinated silicon atom and nonequivalent ligands , 1978 .