Table 2 Data for propene oxide (PO)/phthalic anhydride (PA) ROCOP with Co(III)M(I/II) catalysts

From: Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers

Entry

Catalyst

Time/h

Productivity TONa

Activity TOF/h−1b

Rate coefficient kobs/×10−6 M−1 s−1c

Selectivity polyester/%d

Polyester Mn [Đ]/g mol−1e

1

Co(III)Ca(II)

21

88 ± 2

4 ± 2

17.4 ± 7.4

>99

4600 [1.13]

11600 [1.02]

2

Co(III)Sr(II)

30

87 ± 1

3 ± 1

10.5 ± 3.2

>99

5100 [1.08]

3

Co(III)Ba(II)

30

84 ± 1

3 ± 1

11.2 ± 3.6

>99

6000 [1.11]

4

Co(III)Na(I)

7

88 ± 2

12 ± 1

45.8 ± 1.6

>99

4200 [1.12]

5

Co(III)K(I)

3

89 ± 1

31 ± 1

122.7 ± 4.2

>99

4500 [1.11]

  1. Reaction conditions: Catalyst (0.1 mol%, 0.0143 mM), PA (10 mol%, 1.43 mM), PO (1 mL, 14.3 M), 50 °C (Catalyst:PA:PO, 1:100:1000).
  2. aTON determined by 1H NMR spectroscopy using integrals for PA (8.10–7.85 ppm) and P(PO-alt-PA) (7.75–7.40 ppm).
  3. bTurnover frequency (TOF) is reported from gradients of conversion vs. time plots, from 5 to 20% conversions, in all cases (Supplementary Tables 3 and 4, Supplementary Eq. (2)).
  4. cRate coefficient is the gradient of linear fits to plots of [PA]t vs. time (Supplementary Fig. 36).
  5. dSelectivity for polyester determined by 1H NMR spectroscopy using integrals for P(PO-alt-PA) and any PPO (3.46–3.64 ppm).
  6. eDetermined by GPC, in THF, at 30 °C, using narrow dispersity polystyrene calibrants.
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