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New Bis‐ o ‐Benzoquinoid Ligands with Ethylene Bridge and Their Metal Complexes
Author(s) -
Poddel’sky Andrey I.,
Piskunov Alexander V.,
Druzhkov Nikolay O.,
Fukin Georgii K.,
Cherkasov Vladimir K.,
Abakumov Gleb A.
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900282
Subject(s) - chemistry , ethylene , quinone , medicinal chemistry , metal , benzoquinone , electron paramagnetic resonance , derivative (finance) , crystal structure , thallium , stereochemistry , crystallography , inorganic chemistry , organic chemistry , catalysis , physics , nuclear magnetic resonance , financial economics , economics
The treatment of di‐ o ‐quinone 4,4′‐(ethane‐1,2‐diyl)‐bis(3,6‐di‐ tert ‐butyl‐ o ‐benzoquinone) (Q–CH 2 –CH 2 –Q, 1 ) leads to its rearrangement to form di‐ p ‐quinomethide 4,4′‐(ethane‐1,2‐diylidene)bis(2‐hydroxy‐3,6‐di‐ tert ‐butyl‐cyclohexa‐2,5‐dienone) ( 2 ). The subsequent oxidation of 2 by an alkaline solution of K 3 [Fe(CN) 6 ] yielded the new di‐ o ‐quinone 4,4′‐(ethene‐1,2‐diyl)bis(3,6‐di‐ tert ‐butyl‐ o ‐benzoquinone) (Q–CH=CH–Q, 3 ), which contains an ethylene bridge. The formation of mono‐ and poly‐reduced derivatives of 2 and 3 with potassium, thallium was studied by EPR technique. The dinuclear thallium derivative of 3 , Tl(SQ–CH=CH–SQ)Tl, was found to exist in the diamagnetic quinomethide form. The most stable derivatives of 2 and 3 are triphenyltin(IV) bis‐ p ‐quinomethide‐phenolate ( 4 ) and triphenylantimony(V) bis‐catecholate ( 5 ), which have been synthesized and isolated. The molecular structures of 2 , 3 , and 5 were characterized by single‐crystal X‐ray diffraction.