Synthesis, reactivity and complexation studies of N,S exo-heterodisubstituted o-carborane ligands. Carborane as a platform to produce the uncommon bidentate chelating (pyridine)N-C-C-C-S(H) motif

0518272 - ÚIACH 2020 GB eng J - Journal Article
Teixidor, F. - Laromaine, A. - Kivekas, R. - Sillanpaa, R. - Vinas, C. - Vespalec, Radim - Horáková, Hana
Synthesis, reactivity and complexation studies of N,S exo-heterodisubstituted o-carborane ligands. Carborane as a platform to produce the uncommon bidentate chelating (pyridine)N-C-C-C-S(H) motif.
Dalton Transactions. Č. 3 (2008), s. 345-354. ISSN 1477-9226. E-ISSN 1477-9234
Institutional research plan: CEZ:AV0Z40310501
Keywords : neutron-capture therapy * molecular-structure * capillary-electrophoresis * coordination properties * crystal-structures
OECD category: Analytical chemistry
Impact factor: 3.580, year: 2008
Method of publishing: Limited access

The synthesis of N,S-heterodisubstituted 1-(2 '-pyridyl)-2-SR-1,2-closo-C2B10H10 compounds (R = Et, 2; R = Pr-i, 3) has been accomplished starting from 1-(2 '-pyridyl)-1,2-closo-C2B10H11 (1), and their partial deboronation reaction leading to the structurally chiral [7-(2 '-pyridyl)-8-SR-7,8-nido-C2B9H10](-) derivatives ( R = Et, [ 4]-; R = iPr, [ 5]-) has been studied. Capillary electrophoresis combined with the chiral selector alpha-cyclodextrin has permitted the separation of the electrophoretically pure racemic [7-(2 '-pyridyl)-8-SR-7,8-nido-C2B9H11](-) ions into two peaks each one corresponding to the interaction of one enantiomer with the alpha-cyclodextrin. The N,S-heterodisubstituted o-carborane containing a mercapto group, 1-(2 '-pyridyl)-2-SH-1,2-closo-C2B10H10, 1, is one of the two examples of a rigid bidentate chelating (pyridine) N-C-C-C-S(H) motif having been structurally fully characterized. To study the potential of such a binding site, 1 has been tested as a ligand with metal ions requiring different coordination numbers, two (Au+) and four (Pd2+ and Rh+). The crystal structures of the Pd(II) and Au(I) complexes are reported. For the Pd(II) complex, 1 acts as a bidentate ligand whereas for Au(I), 1 acts as a monodentate ligand through the thiolate.
Permanent Link: http://hdl.handle.net/11104/0303429