Titrations of B(C6F5)3 (1) with water, in toluene-d8 solution, monitored by 19F and 1H NMR at 196 K, showed first the formation of the adduct [(C6F5)3B(OH2)] (2) and then its stepwise transformation into the two aqua species [(C6F5)3B(OH)]·H2O (3) and [(C6F5)3 B(OH2)]·2H2O (4) containing, respectively, one or two water molecules hydrogen-bonded to the protons of the B-bound water molecule. The NMR data show that in each titration step only two species were present in significant concentration: 1 and 2 up to 1 equiv, 2 and 3 between 1 and 2 equiv, 3 and 4 between 2 and 3 equiv. Above 3 equiv the solutions rapidly attained saturation and phase separation occurred (although there was evidence of interaction of 4 with more water molecules). Titrations at room temperature indicated an analogous stepwise course. Variable-temperature experiments demonstrated water exchange between the different aqua species and between the different water sites in the adducts 3 and 4 ("internal" or B-bound and "external" or H-bound). The rate of these processes increased with the amount of water bonded to B(C6F5)3. The exchange of B-bound water among the different B(C6F5)3 molecules (resulting in the 1 ⇔ 2 interconversion) caused the averaging of the 19F resonances of 1 and 2, above 273 K. Band shape analysis in the temperature range 235-312 K provided the kinetic constants, whose dependence on the concentration revealed a dissociative mechanism (ΔH‡ 67(2) kJ mol-1, ΔS‡ 58(7) J mol-1 K-1). For the adduct [(C6F5)3B(OH2)]·H2 O (3), four different dynamic processes have been recognized: (i) the exchange of H-bound water among different [(C6F5)3B(OH2)] adducts (the 2 ⇔ 3 exchange) or (ii) among different [(C6F5)3 B(OH2)]̇H2O adducts (the 3 ⇔ 4 exchange), (iii) the exchange between H-bound and B-bound water, (iv) the hopping of H-bound water between the two protons of B-bound water. This process was so fast that an averaged signal for the protons of internal water was observed even at 187 K. The rate of the process (i) increased with the concentration of 2, so that separate 19F and 1H signals for 2 and 3 were observed only in very dilute solutions at the lowest temperatures. Linear plots of the kinetic constants (estimated from 1H NMR spectra in the near fast exchange region, temperature range 188-214 K) vs the concentration of 2 allowed the estimation of the constant for the dissociative pathway (4 orders of magnitude faster than for the exchange of B-bound water) and for the bimolecular pathway [ΔH‡ 30(2) kJ mol-1, ΔS‡ 3(10) J mol-1 K-1]. Process (ii) was too fast on the NMR time scale to allow any kinetic investigation. Process (iii) caused the parallel broadening of both the 1H signals of 3 at T > 225 K, with a rate quite close to that of the dissociative exchange of water among different B(C6F5)3 molecules. The activation parameters (ΔH‡ 55(2) kJ mol-1, ΔS‡ 7(3) J mol-1 K-1, temperature range 233-273 K) allowed no discrimination between the exchange of an entire water molecule and the mere exchange of protons. Even small amounts of 4 accelerated process (iii), due to the occurrence of two much faster processes: the 3 ⇔ 4 exchange and the exchange between the protons of internal and external water in 4. The study of any kind of water mobility concerning the trihydrate 4 was prevented by the occurrence of proton exchange processes (so fast as to broaden the signals of internal and external water even at 188 K), possibly favored by the acidic dissociation of the protons of the B-bonded water molecule of 4.
1H and 19F investigation of the reaction of B(C6F5)3 with water in toluene solutions / T. Beringhelli, D. Maggioni, G. D'Alfonso. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 20:23(2001), pp. 4927-4938.
|Titolo:||1H and 19F investigation of the reaction of B(C6F5)3 with water in toluene solutions|
BERINGHELLI, TIZIANA (Corresponding)
MAGGIONI, DANIELA (Secondo)
D'ALFONSO, GIUSEPPE (Ultimo)
|Parole Chiave:||olefin polymerization catalysts; ion-pair formation; Lewis-acid tris(pentafluorphenyl)borane; ziegler-type catalysts; zirconium-carbon bond; ray crystal-structure; adduct formation; complexes; betaine; coordination|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||2001|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1021/om010610n|
|Appare nelle tipologie:||01 - Articolo su periodico|