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Chapter 4 101<br />
samples 1a (8% of 5-OH-ip) and 1c (32% of 5-OH-ip) have been selected for testing them<br />
as catalysts for ethylene dimerization. In addition, parent Ru-MOF has been used as a<br />
reference. Thus, activated Ru-DEMOFs were loaded into a reactor to catalyze ethylene<br />
Table 4.7. The conversion of ethylene to butene in toluene under different conditions.<br />
Entry Catalyst (mg) Temperature ( °C) Time (h) Additive TOF (h -1 )<br />
1 1c (2.5) 80 24 ---- 0.92<br />
2 1c (2) 80 1 Et 2 AlCl 4.38<br />
3 1c (2) 80 1 ---- 0.88<br />
4 1c (2.4) 26 2 Et 2 AlCl 2.15<br />
5 1c (2.1) 80 2 Et 2 AlCl 4.36<br />
6 1a (2) 80 2 Et 2 AlCl 2.3<br />
7 Parent Ru-MOF (1.8) 80 2 Et 2 AlCl 2.05<br />
dimerization in toluene at different temperatures under the pressure of 800 psi (≈ 55 bar).<br />
In general, all reactions led to the formation of butene without producing any other α-<br />
olefins (Tables 4.7). Addition of Et2AlCl as co-catalyst accelerates the conversion (Table<br />
4.7, entry 2 vs. entry 3). When the reaction has been conducted at 26 °C, lower yield has<br />
been obtained compared to those at 80 °C (Table 4.7, entry 4 vs. entry 5). However,<br />
reactions conducted for 1 h and 24 h give almost the same TOF (0.88 vs. 0.92 h -1 ),<br />
suggesting that the Ru-DEMOF 1c does not suffer the deactivation as a function of onstream<br />
time. Therefore, parent Ru-MOF and Ru-DEMOFs 1a and 1c have been employed<br />
to study the dimerization of ethylene in toluene under optimized condition (800 psi, 80<br />
°C, 2 h) in the presence of Et2AlCl. The obtained product was analyzed by gas<br />
chromatography. As it can be seen from entry 5-7 in Table 4.7 and Figure 4.37, the TOF<br />
value of 1a and 1c increase along with increase of the incorporation level of DL in<br />
comparison with the parent Ru-MOF. Since the contents of the reduced Ru δ+ -sites in 1c is<br />
the highest among the 1a-d series (according to our study above), there should be more<br />
M-CUSs in 1c and therefore it affords the chance to enhance the catalytic activity in the<br />
reaction. Indeed, the transformation of ethylene to butene is the highest (TOF = 4.36 h -1 )<br />
when employing 1c as a catalyst. This value is still much lower than that using zeolite<br />
supported Ru-complex catalysts in the presence of H2 (4.36 vs. 216 h -1 ). However, it is<br />
higher than the TOF value (1 × 10-4 s -1 = 0.36 h -1 ) in the reported reaction without the
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