. 2022 May 31;61(31):e202201004. doi: 10.1002/anie.202201004

Table 1.

CO conversion (X_CO) and product selectivities (molar carbon base) for slurry‐phase tandem catalysis syngas conversion experiments with different combinations of cobalt solid Fischer–Tropsch synthesis and molecular reductive hydroformylation catalysts, as well as component exclusion reference experiments. Reaction conditions: T=473 K, P=120 bar (initial, measured at RT), stirring rate=700 rpm, syngas feed H₂ : CO=2.0, 2‐methyl pentane as solvent. For tests integrating both FTS and RHF catalysts, catalyst ratio n(Co_FTS)/n(Co_RHF)=170/18 (entry 1.1) or 170/70 (entry 1.4, 1.6–1.9), reaction time t=24 h. For tests where both components forming the RHF catalyst were present the ligand‐to‐metal (L : M) ratio, i.e. P/Co=1 : 1 (at/at). Ligand abbreviations: [1] PCy₃: tricyclohexyl phosphine. [2] PPh₃: triphenyl phosphine. [3] P(n‐Bu)₃: tri‐n‐butyl phosphine.

Entry	Catalyst		X_CO	S(CO₂)	S(CH₄)	S _C5+	α_HC ^[a]	S _olef.	S _ROH	S _{C5+ ROH}	ROH^[b]	α_ROH ^[c]
	FTS	RHF	[%]	[C%]	[C%]	[C%]	[C%]	[C%]	[C%]	[C%]	n : iso	[−]
1.1	NaPr‐CoRu/AOmM	Co₂CO₈ + PCy₃ ^[1]	35.1	1.8	10.3	66.9	0.71	0.1	37.0	25.4	4.2	0.58
1.2	NaPr‐CoRu/AOmM	–	36.1	1.5	6.3	64.9	0.66	0.2	25.5	12.6	2.2	0.54
1.3	NaPr‐CoRu/AOmM	PCy₃	21.8	1.1	9.5	55.4	0.63	0.1	33.6	15.8	6.4	0.44
1.4	NaPr‐CoRu/AOmM	Co₂CO₈	41.8	1.6	9.4	50.6	0.64	0.8	19.5	9.2	2.1	0.54
1.5	–	Co₂CO₈+PCy₃	0.2	>60	>20	<0.1	n.a.	0.0	0.0	0.0	n.a.	n.a.
1.6	NaPr‐CoRu/AOmM	Co₂CO₈+PPh₃ ^[2]	28.8	2.3	8.6	55.3	0.70	<0.1	47.7	25.4	3.1	0.57
1.7	NaPr‐CoRu/AOmM	Co₂CO₈+(P(n‐Bu)₃) ^[3]	26.8	4.9	8.9	53.8	0.69	<0.1	53.9	30.5	4.6	0.53
1.8	NaPr‐CoRu/AOmM	Co₂CO₈+PCy₃	34.0	2.2	6.9	59.1	0.71	<0.1	53.7	22.7	5.8	0.61
1.9	CoRu/AOm	Co₂CO₈+PCy₃	24.5	1.1	9.4	74.5	0.84	<0.1	32.7	23.3	4.4	0.66

[a] Hydrocarbon chain‐growth probability. [b] Alcohol linear‐to‐branched molar ratio. [c] Alcohol chain‐growth probability.