Premium
The (Tetraazaannulene)copper‐Catalyzed Reduction of Sulfur(IV) Species. A Pulse‐Radiolysis and Theoretical Study of the Associated Reaction Mechanism
Author(s) -
Ferraudi Guillermo,
Estiu Guillermina,
Lappin A. Graham,
Villagran Manuel,
Muena Juan P.,
Costamagna Juan,
Zagal Jose
Publication year - 2009
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200800319
Subject(s) - chemistry , disproportionation , radiolysis , adduct , copper , catalysis , sulfur , electrochemistry , monomer , inorganic chemistry , photochemistry , crystallography , aqueous solution , organic chemistry , electrode , polymer
The monomeric species, [Cu II {H x (tmdnTAA)}] x + ( x =0, 1, and 2, and (tmdnTAA) 2− =[5,7,12,14]tetramethyldinaphtho[ b , i ][1,4,8,11]tetraaza[14]annulenato(2−)=7,9,18,20‐tetramethyldinaphtho[2,3‐ b : 2′,3′‐ i ] [1,4,8,11]tetraazacyclotetradecinato(2−)) catalyze the electrochemical reduction of SO 2 (aq) in homogeneous solution. A pulse‐radiolytic study of the reaction of the [Cu I (tetraazaannulene)] complexes with S IV species revealed the formation of Cu I SO 2 adducts. The formation of Cu I SO 2 adducts prevents the disproportionation of the Cu I complexes and precedes the reduction of the S IV species to S 2 O $\rm{ _4^{2 - } }$ . DFT Calculations were carried out to establish the structure and stability of the Cu I SO 2 adducts. A good agreement between the calculated and recorded electronic spectrum of the Cu I SO 2 adducts corroborated the formation of species with SO 2 coordinated to Cu I through the O‐atom.