Premium
Tin(IV) and Antimony(V) Complexes Bearing Catecholate Ligands Connected to Ferrocene – Syntheses, Molecular Structures, and Electrochemical Properties
Author(s) -
Baryshnikova Svetlana V.,
Bellan Ekaterina V.,
Poddel'sky Andrey I.,
Arsenyev Maxim V.,
Smolyaninov Ivan V.,
Fukin Georgy K.,
Piskunov Alexander V.,
Berberova Nadezhda T.,
Cherkasov Vladimir K.,
Abakumov Gleb A.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600885
Subject(s) - chemistry , ferrocene , catechol , imine , cyclic voltammetry , medicinal chemistry , intramolecular force , tetrahydrofuran , toluene , nuclear magnetic resonance spectroscopy , tin , electrochemistry , polymer chemistry , stereochemistry , organic chemistry , solvent , catalysis , electrode
The ferrocenyl‐containing 3,5‐di‐ tert ‐butylcatechol Fc‐L‐CatH 2 ( 2 ) was synthesized by the condensation of the precursor 6‐(hydrazonomethyl)‐3,5‐di‐ tert ‐butylcatechol 6‐(H 2 N–N=CH)CatH 2 ( 1 ) with ferrocenecarboxaldehyde (L = –CH=N–N=CH–, Cat = 3,5‐di‐ tert ‐butylcatecholate, Fc = ferrocene). The exchange reaction between catechol 2 and Ph 3 SbBr 2 in the presence of a base (Et 3 N) in toluene leads to the formation of the triphenylantimony(V) catecholate (Fc‐L‐Cat)SbPh 3 ( 3 ) as the main product and the ionic bromotriphenylantimony(V) catecholate (Fc‐LH‐Cat)SbPh 3 Br ( 4 ) containing a hydraziniumylidene cation (LH = –CH=NH + –N=CH–) as the byproduct. The change of toluene to tetrahydrofuran (THF) results in the formation of 4 as the main product in nearly quantitative yield. The exchange reactions of catechol 2 with Ph 2 SnCl 2 and SnCl 4 give anionic catecholate complexes bridged with hydraziniumylidene cations even in the presence of excess base. Complexes (Fc‐LH‐Cat)SnPh 2 Cl ( 5 ), (Fc‐LH‐Cat) 2 SnPh 2 ( 6 ), and (Fc‐LH‐Cat) 2 SnCl 2 ( 7 ) were synthesized. The compounds obtained were characterized by IR spectroscopy, 1 H and 13 C NMR spectroscopy, elemental analysis, and cyclic voltammetry. The molecular structures of crystals of 5 – 7 were determined by X‐ray diffraction analysis. The formation of catecholates 4 – 7 with hydraziniumylidene cations is caused by intramolecular hydrogen bonding between the hydroxy and imine groups, which leads to proton transfer from the oxygen atom to the nitrogen atom of the hydrazine linker.