Reactivity of the organometallic fac-[(CO)3ReI(H2O)3]+ aquaion. Kinetic and thermodynamic properties of H2O substitution.
The water exchange process on [(CO)(3)Re(H(2)O)(3)](+) (1) was kinetically investigated by (17)O NMR. The acidity dependence of the observed rate constant k(obs) was analyzed with a two pathways model in which k(ex) (k(ex)(298) = (6.3 +/- 0.1) x 10(-3) s(-1)) and k(OH) (k(OH)(298)= 27 +/- 1 s(-1)) denote the water exchange rate constants on 1 and on the monohydroxo species [(CO)(3)Re(I)(H(2)O)(2)(OH)], respectively. The kinetic contribution of the basic form was proved to be significant only at [H(+)] < 3 x 10(-3) M. Above this limiting [H(+)] concentration, kinetic investigations can be unambiguously conducted on the triaqua cation (1). The variable temperature study has led to the determination of the activation parameters Delta H(++)(ex) = 90 +/- 3 kJ mol(-1), Delta S(++)(ex) = +14 +/- 10 J K(-1) mol(-1), the latter being indicative of a dissociative activation mode for the water exchange process. To support this assumption, water substitution reaction on 1 has been followed by (17)O/(1)H/(13)C/(19)F NMR with ligands of various nucleophilicities (TFA, Br(-), CH(3)CN, Hbipy(+), Hphen(+), DMS, TU). With unidentate ligands, except Br(-), the mono-, bi-, and tricomplexes were formed by water substitution. With bidentate ligands, bipy and phen, the chelate complexes [(CO)(3)Re(H(2)O)(bipy)]CF(3)SO(3) (2) and [(CO)(3)Re(H(2)O)(phen)](NO(3))(0.5)(CF(3)SO(3))(0.5).H(2)O (3) were isolated and X-ray characterized. For each ligand, the calculated interchange rate constants k'(i) (2.9 x 10(-3) (TFA) < k'(I) < 41.5 x 10(-3) (TU) s(-1)) were found in the same order as the water exchange rate constant k(ex), the S-donor ligands being slightly more reactive. This result is indicative of I(d) mechanism for water exchange and complex formation, since larger variations of k'(i) are expected for an associatively activated mechanism.
Salignac
Bernadette
B
Ecole Polytechnique Fédérale de Lausanne, Institut de Chimie Moléculaire et Biologique, BCH, CH-1015 Lausanne, Switzerland.
Grundler
Pascal V
PV
Cayemittes
Sonia
S
Frey
Urban
U
Scopelliti
Rosario
R
Merbach
André E
AE
Hedinger
Roman
R
Hegetschweiler
Kaspar
K
Alberto
Roger
R
Prinz
Ulrich
U
Raabe
Gerhard
G
Kölle
Ulrich
U
Hall
Syd
S