A solution and solid state study of niobium complexes University of ...

Appendix B
Appendix B
B 1 Supplementary Data for the formation kinetics of [NbCl(acac)
(OMe)3]:
Table B.1: Data collected on the Stopped-flow following the formation reaction of
[NbCl(acac)(OMe)3] in MeOH, (λ = 330 nm; [Nb] = 5 x10 -5 M).
[acac] (M)
15 °C
kobs (s
25 °C 35 °C 45 °C
-1 ) kobs (s -1 ) kobs (s -1 ) kobs (s -1 )
0.0005 0.101 0.2389 0.573 1.39
0.001 0.1472 0.3738 0.869 2.151
0.0025 0.2864 0.6977 1.736 4.22
0.0035 0.402 0.969 2.29 5.63
0.004 0.4362 1.083 2.61 6.44
0.005 0.532 1.307 3.152 7.924
Table B.2: Data collected on the CARY following the formation reaction of
[NbCl(acac)(OMe)3] in MeOH, (λ = 310 nm; [Nb] = 5 x10 -5 M).
15 °C 25 °C 35 °C 45 °C
[acac] (M) kobs (x 10 -5 )
(s -1 kobs (x 10
)
-5 )
(s -1 kobs (x 10
)
-5 )
(s -1 kobs (x 10
)
-5 )
(s -1 )
0.0005 1.52 3.31 7.5 17.03
0.001 1.79 3.92 8.63 19.72
0.0025 2.07 4.71 10.7 22.19
0.0035 2.17 4.8 10.9 23.14
0.004 2.18 4.92 11.1 23.82
0.005 2.24 5.02 11.2 23.66
Table B.3: ln(k/T) and 1/T values for both reactions, as used for the Eyring plot.
1/T (K -1 ) lnk1/T lnk2/T
0.003143 1.5099 -14.5673
0.003245 0.622 -15.164
0.003354 -0.2295 -15.902
0.00347 -1.0991 -16.76
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