Table 2.
NA/CHO ROCOP data using catalysts 1–8 and compared against leading catalysts from the literature (See Figure 1 for reaction scheme).[a]
|
Entry |
[LMg(II)M(II)(OAc)2] M, cat # |
Conv. [%][b] |
Polymer [%][c] |
TON[d] |
TOF [h−1][e] |
k p′ [mM−1 s−1][f] |
k rel′[g] |
M n [kg mol−1] [Ð][h] |
|---|---|---|---|---|---|---|---|---|
|
1 |
Mg, 1 |
>99 |
>99 |
100 |
71 (±4) |
8.7 (±0.5) |
1.0 |
1.6 [1.15] |
|
2 |
Cr, 2 |
>99 |
>99 |
100 |
54 (±3) |
6.6 (±0.4) |
0.8 |
n.d |
|
3 |
Mn, 3 |
>99 |
>99 |
100 |
272 (±13) |
33.5 (±1.6) |
3.9 |
1.4 [1.14] |
|
4 |
Fe, 4 |
>99 |
>99 |
100 |
109 (±5) |
13.4 (±0.6) |
1.5 |
1.3 [1.15] |
|
5 |
Co, 5 |
>99 |
>99 |
100 |
610 (±31) |
75.2 (±3.8) |
8.6 |
1.5 [1.14] |
|
6 |
Ni, 6 |
>99 |
>99 |
100 |
244 (±12) |
30.1 (±1.5) |
3.5 |
1.4 [1.15] |
|
7 |
Cu, 7 |
>99 |
>99 |
100 |
170 (±9) |
21.2 (±1.1) |
2.4 |
1.2 [1.15] |
|
8 |
Zn, 8 |
>99 |
>99 |
100 |
186 (±10) |
23.0 (±1.2) |
2.6 |
1.3 [1.14] |
|
9[i][52] |
(ONSO)CrCl/PPNCl |
97 |
>99 |
243 |
360 |
– |
– |
11.9 [1.28] |
|
10[j][50] |
(salophen)CrCl/DMAP |
97 |
>99 |
243 |
49 |
– |
– |
3.0 [1.12] |
|
11[k][13a] |
(salen[CyPr]+)AlCl2 |
51 |
>99 |
204 |
34 |
– |
– |
8.2 [1.24] |
|
12[l][53] |
(o‐van)AlK(OAc)2 |
33 |
>99 |
133 |
266 |
– |
– |
4.5 [1.10] |
|
13[m] |
Co |
>99 |
>99 |
100 |
666 (±21) |
|
– |
2.2 [1.14] |
[a] Reaction conditions: [cat]0:[CHD]0:[NA]0:[CHO]0=1 : 20 : 100 : 2000; 0.05 mol% catalyst loading (4.88 mM), 20 equivalents trans‐1,2‐cyclohexendiol (97.6 mM), neat CHO (3.2 mL, 9.9 M), 100 °C. [b] Expressed as a percentage of epoxide conversion against the theoretical maximum (100 %). [c] Expressed as a percentage of polymer selectivity against cyclic carbonate formation. [d] Turn over number (TON)=number of moles of monomer converted/number of moles of catalyst. [e] Turn over frequency (TOF)=TON/hour. [f] k p=rate coefficient=k obs/[cat]1 where k obs is calculated from the gradient of the plot of [NA] vs. time (s). [g] k rel=relative rate coefficient=k p(MgM)/k p(MgMg). [h] Determined by SEC analysis, in THF, calibrated with narrow‐M n polystyrene standard; dispersity values in parentheses. [i] Reaction conditions: [cat]0/[PPNCl]0:[NA]0:[CHO]0=1 : 1 : 250 : 250 in toluene (2 mL), 110 °C. [j] Reaction conditions: [cat]0:[DMAP]0:[NA]0:[CHO]0=1 : 1 : 250 : 250 in toluene, 110 °C. [k] Reaction conditions: [cat]0:[NA]0:[CHO]0=1 : 400 : 2000, 0.05 mol % catalyst loading, neat CHO (9.9 M), 60 °C. [l] Reaction conditions: [cat]0:[NA]0;[CHO]0=1 : 400 : 2000, 0.05 mol %, neat CHO (9.9 M), 100 °C. [m] Reaction with Phthalic Anhydride (PA). For reported catalyst structures, entries 9–13, see Figure S31.