TY - JOUR
T1 - Facile cobalt(III) template synthesis of novel branched hexadentate polyamine monocarboxylates
AU - Barfod, Rasmus
AU - Eriksen, Jette
AU - Golding, Bernard T.
AU - Hammershøi, Anders
AU - Jacobsen, Thomas Amos
AU - Langkilde, Annette
AU - Larsen, Sine
AU - Mønsted, Ole
AU - Sargeson, Alan M.
AU - Sørensen, Henning Osholm
PY - 2005/2/7
Y1 - 2005/2/7
N2 - New hexadentate polyamine monocarboxylate ligands, 11-amino-9-(2- aminoethyl)-3,6,9-triazaundecanoate (tren-engly-), 12-amino-10-(2-aminoethyl)-3,7,10-triazadodecanoate (tren-tngly-) and 13-amino-11 (2-aminoethyl)-3,8,11-triazatridecanoate (tren-bngly-), were synthesized by intramolecular coupling of tetradentate tris(2-aminoethyl) amine (tren) and didentate N-(ω-formylalkyl)glycinates, OCH(CH 2)n,NHCH2CO2-, in easily and stereoselectively assembled cobalt(III) templates, p-[Co(tren){(RO) 2CH(CH2)nNHCH2CO2}] (O3SCF3)2, n= 1-3 (R = Me or Et). The reaction sequences comprised assembly of the template from [Co(tren)(O 3SCF3)2]O3SCF3 (1) and (RO)2CH(CH2)nNHCH2CO2Et, deprotection of the pendant acetal in acid, intramolecular condensation of the resulting aldehyde with a coordinated primary amine at intermediate pH to form the inline and reduction of this by NaBH4. For n = 1, imine formation occurred exclusively at the primary amine trans to the carboxylate producing the hexadentate 11-amino-9-(2-aminoethyl)-3,6,9-triazaundeca-5-enoato (tren-enimgly-) complex, i-[Co(trenenimgly)]Cl2̇3. 5H2O. In all instances, subsequent imine reduction gave the s isomer complex, exclusively. Complexes p-[Co(tren){(MeO)2CHCH 2gly}](O3SCF3)2 (3), i-[Co(tren-enimgly)]ZnCl4̇H2O (5), s-[Co(tren-engly)]ZnCl4 (s-6), s-[Co(tren-tngly)]ZnCl 4̇H2O (s-7) and s-[Co(tren-bngly)ZnCl 3]2ZnCl4 (s-8) were structurally characterized by X-ray crystallography. Charcoal-catalyzed equilibration of s-[Co(tren-engly)]Cl2̇2H2O dissolved in water produced the s- (s-6), p- (p-6) and t-[Co(tren-engly)]2+ (t-6) isomers in comparable amounts, p-6 and t-6 were also structurally characterized as their tetrachlorozincate and chloride salts, respectively. In base-catalyzed reactions, s-6 and t-6 each also formed p-6. Reduction of s-[Co(tren-engly)] Cl2̇2H2O with (NH4)2S and acidification liberated the pentaamino carboxylic acid ligand which was isolated as the hydrochloride salt.
AB - New hexadentate polyamine monocarboxylate ligands, 11-amino-9-(2- aminoethyl)-3,6,9-triazaundecanoate (tren-engly-), 12-amino-10-(2-aminoethyl)-3,7,10-triazadodecanoate (tren-tngly-) and 13-amino-11 (2-aminoethyl)-3,8,11-triazatridecanoate (tren-bngly-), were synthesized by intramolecular coupling of tetradentate tris(2-aminoethyl) amine (tren) and didentate N-(ω-formylalkyl)glycinates, OCH(CH 2)n,NHCH2CO2-, in easily and stereoselectively assembled cobalt(III) templates, p-[Co(tren){(RO) 2CH(CH2)nNHCH2CO2}] (O3SCF3)2, n= 1-3 (R = Me or Et). The reaction sequences comprised assembly of the template from [Co(tren)(O 3SCF3)2]O3SCF3 (1) and (RO)2CH(CH2)nNHCH2CO2Et, deprotection of the pendant acetal in acid, intramolecular condensation of the resulting aldehyde with a coordinated primary amine at intermediate pH to form the inline and reduction of this by NaBH4. For n = 1, imine formation occurred exclusively at the primary amine trans to the carboxylate producing the hexadentate 11-amino-9-(2-aminoethyl)-3,6,9-triazaundeca-5-enoato (tren-enimgly-) complex, i-[Co(trenenimgly)]Cl2̇3. 5H2O. In all instances, subsequent imine reduction gave the s isomer complex, exclusively. Complexes p-[Co(tren){(MeO)2CHCH 2gly}](O3SCF3)2 (3), i-[Co(tren-enimgly)]ZnCl4̇H2O (5), s-[Co(tren-engly)]ZnCl4 (s-6), s-[Co(tren-tngly)]ZnCl 4̇H2O (s-7) and s-[Co(tren-bngly)ZnCl 3]2ZnCl4 (s-8) were structurally characterized by X-ray crystallography. Charcoal-catalyzed equilibration of s-[Co(tren-engly)]Cl2̇2H2O dissolved in water produced the s- (s-6), p- (p-6) and t-[Co(tren-engly)]2+ (t-6) isomers in comparable amounts, p-6 and t-6 were also structurally characterized as their tetrachlorozincate and chloride salts, respectively. In base-catalyzed reactions, s-6 and t-6 each also formed p-6. Reduction of s-[Co(tren-engly)] Cl2̇2H2O with (NH4)2S and acidification liberated the pentaamino carboxylic acid ligand which was isolated as the hydrochloride salt.
UR - http://www.scopus.com/inward/record.url?scp=20044380335&partnerID=8YFLogxK
U2 - 10.1039/b416994h
DO - 10.1039/b416994h
M3 - Article
SN - 1477-9226
SP - 491
EP - 500
JO - Dalton Transactions
JF - Dalton Transactions
IS - 3
ER -