Table 3 Substrate scope of the Co-catalysed hydroformylation of olefins without directing groups with MOF additives and comparison with the homogeneously catalysed reaction^a,b.


Entry	Olefin	MixUMCM-1-NH₂ (28%)^a,c B/L\|Conv. (%) [Oxo yield (%)]	MOF-74(Zn)^a,d B/L\|Conv. (%) [Oxo yield (%)]	No MOF^a B/L\|Conv. (%) [Oxo yield (%)]
1		83/17\|75 [60]	90/10\|85 [70]	61/39\|99 [95]
2		79/21\|62 [55]	89/11\|86 [75]	52/48\|97 [95]
3		84/16\|84 [80]	86/14\|81 [75]	54/46\|97 [95]
4		77/23\|80 [75]	83/17\|71 [65]	61/38\|>99 [95]
5		70/30\|15 [10]^j	81/19\|49 [40]^k	60/40\|58 [50]^l

^aConv. = olefins conversion; Oxo yield = yield of oxo products. B/L and conversion were calculated using GC-FID with p-cymene as external standard. Oxo products yield was calculated by combining the mass of the raw product after reaction and the purity determined by GC-FID (see Supplementary Information). The oxo products were identified as aldehydes (Supplementary Table 10) and aldol condensation products.
^bCo₂(CO)₈ (1.5 mol%) were dissolved in olefin (500 µL) and the MOF was added. The mixture was brought to 30 bar and then heated to 100 °C for 17 h.
^cmol_MOF/mol_Co = 0.4.
^dmol_MOF/mol_Co = 3.3.
^e1:2:3 ratio (homogeneous and MixUMCM-1-NH₂) = 3:1:0. 1:2 ratio (MOF-74(Zn)) = 2:1:0.
^f1:2:3 ratio = 7:2:1.
^g1:2:3 ratio = 7:2:1.
^h1:2:3 ratio = 6:2:2.
ⁱ1:2:3 ratio = 7:1.5:1.5.
^jEleven per cent of hydrogenated olefin was detected by GC-FID and GC-MS.
^kTen per cent of hydrogenated olefin was detected by GC-FID and GC-MS.
^lFive per cent of hydrogenated olefin was detected by GC-FID and GC-MS.

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Entry	Olefin	MixUMCM-1-NH₂ (28%)^a,c B/L\|Conv. (%) [Oxo yield (%)]	MOF-74(Zn)^a,d B/L\|Conv. (%) [Oxo yield (%)]	No MOF^a B/L\|Conv. (%) [Oxo yield (%)]
1		83/17\|75 [60]	90/10\|85 [70]	61/39\|99 [95]
2		79/21\|62 [55]	89/11\|86 [75]	52/48\|97 [95]
3		84/16\|84 [80]	86/14\|81 [75]	54/46\|97 [95]
4		77/23\|80 [75]	83/17\|71 [65]	61/38\|>99 [95]
5		70/30\|15 [10]^j	81/19\|49 [40]^k	60/40\|58 [50]^l

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