Table 1 Summary of isomerization kinetics

From: Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

macrocycle

T (°C)

ΔG‡expta,b

ΔG‡calcc

(S,R)-E(2,2)

69–84

27.0 ± 2.0

26.1*, 23.7

[(S,R)-E(2,2)]PtCl2

−10–6

20.3 ± 2.0

18.7*, 18.0

(S,R)-E(2,3)

120–135

31.0 ± 2.0

29.6*, 30.4

[(S,R)-E(2,3)]PtCl2

64–80

26.7 ± 1.9

26.4*, 24.7

(S,S)-E(3,3)

131

31.4 ± 0.1d

33.8d

[(S,S)-E(3,3)]PtCl2

125

30.0 ± 0.1e

29.7e

(S,R)-E(3,3)

128

31.0 ± 0.1f

32.7f

[(S,R)-E(3,3)]PtCl2

121

29.6 ± 0.1g

32.1g

  1. The measured (ΔG‡expt) and calculated (ΔG‡calc) activation free energies of stiff stilbene E → Z isomerization in E(m,n) macrocycles and their platinum complexes [E(m,n)]PtCl2 in kcal/mol.
  2. aat 298 K unless noted otherwise.
  3. bfree ligand in p-xylene-d10; metal complex in DMF-d7.
  4. cat 298 K unless specified otherwise, in vacuum at 1 atm; the two values for E(2,n), n = 2 or 3 correspond to the (S,R) and (S,S) diastereomers where * indicates the more stable diastereomer.
  5. dT = 131 °C.
  6. eT = 125 °C.
  7. fT = 128 °C.
  8. gT = 125 °C.
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