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Multicomponent assembly of anionic and neutral decanuclear copper(II) phosphonate cages
V. Chandrasekhar, L. Nagarajan, S. Hossain, K. Gopal, , S. Verma
Published in
2012
Volume: 51
   
Issue: 10
Pages: 5605 - 5616
Abstract
A multicomponent synthetic strategy involving copper(II) ions, tert-butylphosphonic acid (t-BuPO 3H 2) and 3-substituted pyrazole ligands has been adopted for the synthesis of soluble molecular copper(II) phosphonates. The use of six different 3-substituted pyrazoles, 3-R-PzH [R = H, Me, CF 3, Ph, 2-pyridyl (2-Py), and 2-methoxyphenyl (2-MeO-C 6H 4)] as ancillary ligands afforded nine different decanuclear cages, [Cu 5(μ 3-OH) 2(O 3P-t-Bu) 3(3-R-Pz) 2(X) 2] 2·(Y) where R = H, X = t-BuPO 3H, and Y = (Et 3NH +) 4(solvent) (1); R = Me, X = 3-MePzH, and Y = solvent (2); R = Me, X = t-BuPO 3H, and Y = (Et 3NH +) 4(solvent) (3); R = CF 3, X = t-BuPO 3H, and Y = (Et 3NH +) 4(solvent) (4); R = Ph, X = 3-PhPzH, and Y = solvent (5); R = 2-Py, X = 0.5 MeOH, and Y = solvent (6); R = 2-Py, X = none, and Y = solvent (7); R = 2-Py, X = H 2O, and Y = (Et 3NH +·PF 6 -) 2(solvent) (8); R = 2-MeO-C 6H 4, X = MeOH or 0.5:0.5 MeOH/H 2O, and Y = solvent (9). Compounds 1-6, 8, and 9 were isolated using a direct synthetic method which involves the reaction of copper(II) salts and the ligands, while 7 was obtained from an indirect route involving the reaction of preformed copper-pyridylpyrazolate precursor complexes and t-BuPO 3H 2. The decametallic compounds 1-9 possess a butterfly shaped core. The core of the cages 1, 3, and 4 are tetraanionic and contain more phosphonates than pyrazole ligands, while the other cages are neutral and contain more pyrazoles than phosphonate ligands. Compounds 1-6 have been studied by electrospray ionization-high-resolution mass spectrometry (ESI-HRMS). The decanuclear cage 6 was shown to be a good plasmid modifier. © 2012 American Chemical Society.
About the journal
JournalInorganic Chemistry
ISSN00201669