Romero Nuria, Vendier Laure, Dinoi Chiara, Etienne Michel
CNRS, LCC (Laboratoire de Chimie de Coordination), BP 44099, 205 route de Narbonne, F-31077 Toulouse Cedex 4, France.
Dalton Trans. 2014 Jul 14;43(26):10114-9. doi: 10.1039/c4dt00884g. Epub 2014 May 29.
Two series of highly fluorinated 3-substituted hydrotris(indazolyl)borate (Fn-Tp(4Bo,3R); R = Ph, n = 12; R = CF3, n = 21) complexes of calcium were synthesized by salt metathesis reactions. CaI2 reacts with 2 and 1 equiv. of Tl(F12-Tp(4Bo,3Ph)) in THF to form the homo- and heteroleptic complexes [Ca(F12-Tp((4Bo,3Ph)*))2] (1) and [(F12-Tp(4Bo,3Ph))CaI(THF)] (2), respectively. 1 has C2h symmetry due to a 1,2-borotropic shift. The reaction of CaI2 with 2 equiv. of the more electron poor Tl(F21-Tp(4Bo,3CF3)) in THF, on the other hand, leads to the salt [Ca(THF)6][F21-Tp(4Bo,3CF3)]2 (3), with [F21-Tp(4Bo,3CF3)] acting as a counter-ion. This emphasizes the tuning ability of Fn-Tp(4Bo,3R) ligands and the consequences on their ability to bind hard electrophilic Ca(2+) centers.
