Thermodynamic and activation parameters for dissociation of [CpCr(CO)(3)](2) and [Cp*Cr(CO)(3)](2) into paramagnetic monomers from H-1 NMR shift and line width measurements
Dc. Woska et al., Thermodynamic and activation parameters for dissociation of [CpCr(CO)(3)](2) and [Cp*Cr(CO)(3)](2) into paramagnetic monomers from H-1 NMR shift and line width measurements, INORG CHEM, 38(18), 1999, pp. 4135-4138
H-1 NMR spectra for solutions prepared by dissolution of [CpCr(CO)(3)](2) a
nd [Cp*Cr(CO)(3)](2) in toluene in the temperature range 190-390 K are inte
rpreted in terms of thermodynamic and kinetic parameters for dissociation o
f the diamagnetic dimers into the paramagnetic monomers CpCr(CO)(3) and Cp*
Cr(CO)(3). There is no evidence in this temperature range for thermally pop
ulated excited states or non-Curie magnetic behavior of the monomers making
a significant contribution to the NMR. An expression for the temperature d
ependence of the NMR chemical shift at limiting fast interchange of monomer
and dimer in terms of the Delta H degrees and Delta S degrees for dimer di
ssociation is applied in determining the thermodynamic parameters for Cr-Cr
bond homolysis of [CpCr(CO)(3)](2) (Delta H(1)degrees = 15.3 +/- 0.6 kcal
mol(-1); Delta S(1)degrees = 39 +/- 2 cal K-1 mol(-1)) and [Cp* Cr(CO)(3)](
2) (Delta H(2)degrees = 14.2 +/- 0.4 kcal mol(-1); Delta S(2)degrees = 47 /- 2 cal K-1 mol(-1)). Rate constants and activation parameters have been e
valuated from H-1 NMR line broadening in the region of slow dimer-monomer i
nterchange for dissociation of [CpCr(CO)(3)](2) (k(1) (240 K) approximate t
o 59 s(-1); Delta H(1)double dagger = 17 +/- 2 kcal mol(-1); Delta S(1)doub
le dagger = 21 +/- 6 cal K-1 mol(-1)) and [Cp*Cr(CO)(3)](2) (k(2) (240K) ap
proximate to 1.4 x 10(4) s(-1); Delta H(2)double dagger = 16 +/- 1 kcal mol
(-1); Delta S(2)double dagger = 30 +/- 6 cal K-1 mol(-1)): Paramagnetic shi
fts also were used in deriving electron-proton coupling constants (A(H)) fo
r CpCr(CO)(3) (8.22 x 10(5) Hz) and Cp*Cr(CO)(3) (1.33 x 10(6) Hz).