Supplementary Information

Butadiene hydroformylation to adipaldehyde with Rh-based catalysts:

insights into ligand effects

Simin Yu1, William K. Snavely1, Raghunath V. Chaudhari1,2, and Bala Subramaniam1,2*

1Center for Environmentally Beneficial Catalysis, The University of Kansas, Lawrence,

KS, 66047, USA.

2Department of Chemical and Petroleum Engineering, The University of Kansas,

Lawrence, KS 66045, USA.

*Corresponding author. Tel.: +1-785-864-2903. Fax:+1-785-864-6051.

E-mail: bsubramaniam@ku.edu

Contents

A. Experimental apparatus

B. Carbon balance

C. Product quantification

D. Turnover frequency calculation

E. Reaction parameter effects on butadiene hydroformylation

F. Ligand effect on butadiene or 4-pentenal hydroformylation

G. ReactIR experiment

H. Reference

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A. Experimental apparatus

Fig. S1. Schematic of experimental unit.

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B. Carbon balance

Table S1: Hydroformylation of butadiene catalyzed by (CO)2Rh(acac) with DIOP. Reaction conditions: 15 mL toluene, 80 C, 260 min, 1000 rpm.

EntrynC(feed) / mmol nC(end-of-run products) / mmol Carbon

balance %COa Butadienei Total Butadienef

Aldehydeproducts Total

1 6.9 22.8 29.7 0 26.0 26.0 88

2 7.4 22.8 30.2 0.2 28.2 28.4 94

3 7.2 22.8 30.0 0.2 28.2 28.4 94

4 7.7 22.8 30.5 0 29.6 29.6 97

5 7.2 22.8 30.0 0.3 28.6 28.9 96

6 16.0 45.6 61.6 0.5 58.4 58.9 96

7 1.8 4.6 6.4 0 5.7 5.7 89

8 8.3 22.8 31.1 0.3 29.9 30.2 97

9 7.7 22.8 30.5 0.3 28.3 28.6 94anC(CO) is calculated using Eq. 5.

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Table S2: Carbon balance for butadiene hydroformylation. Reaction conditions: 5.7 mmol butadiene, 0.04 mmol (CO)2Rh(acac), molar [P/Ph] ratio = 6, syngas pressure = 14 bar; molar [H2/CO] ratio = 1, 15 mL toluene, 80 C, 260 min, 1000 rpm.

Entry LigandnC(feed) / mmol nC(end-of-run products) / mmol Carbon

balance %COa Butadienei Total Butadienef

Aldehydeproducts Total

1 DPPE 6.7 22.8 29.5 0.3 23.3 23.6 80

2 DPPP 6.1 22.8 28.9 1.4 22.0 23.4 81

3 DPPB 7.4 22.8 30.2 0.3 26.2 26.5 88

4 DPPF 7.9 22.8 30.7 0.3 26.7 27.0 89

5 DIOP 7.9 22.8 30.7 0.2 28.6 28.8 94

6 6-DPPon 6.8 22.8 29.6 0 25.8 25.8 87

7 Xantphos 5.6 22.8 28.4 0.4 23.6 24.0 858 Biphephos 2.1 22.8 24.9 11.9 9.8 21.7 87

anC(CO) is calculated using Eq. 5.

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Table S3: Carbon balance for 4-pentenal hydroformylation. Reaction conditions: 1.8 mmol 4-pentenal, 0.016 mmol (CO)2Rh(acac), molar [P/Ph] ratio = 6, syngas pressure = 14 bar; molar [H2/CO] ratio = 1, 15 mL toluene, 80 C, 80 min, 1000 rpm.

Entry LigandnC(feed) / mmol nC(end-of-run products) / mmol Carbon

balance %COa 4-pentenali Total 4-pentenalf

Aldehydeproducts Total

1 DPPE 0.8 9.2 10.0 4.1 4.7 8.8 88

2 DPPP 0.3 9.2 9.5 6.0 2.7 8.7 92

3 DPPB 1.7 9.2 10.9 2.1 8.7 10.8 99

4 DPPF 1.4 9.2 10.6 3.1 6.9 10.0 94

5 DIOP 1.6 9.2 10.8 1.6 10.7 11.5 106

6 6-DPPon 1.9 9.2 11.1 0.0 12.1 12.1 109

7 Xantphos 1.5 9.2 10.7 1.6 9.6 11.2 105

8 Biphephos 1.8 9.2 11.0 0.0 12.0 12.0 109anC(CO) is calculated using Eq. 5.

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C. Product quantification

Fig. S2. Calibration curves for 4-pentenal (left) and adipaldehyde (right).

As shown in Fig. S2, we constructed GC calibration curves for 4-pentenal and

adipaldehyde by using decane as the internal standard. Adipaldehyde was synthesized

following literature procedure.[2] The purities of 4-pentenal and adipaldehyde were

determined based on 1H NMR spectrum and this value was then used to prepare the

calibration curve. The FID response factor of 4-pentenal and adipaldehyde were obtained

as 0.627 and 0.336. These values are close to the literature results summarized in Table

S1. Since not all the products are commercially available, we use the literature FID

response factors for product quantification. Typical retention times in our experiments

and FID response factors reported in the literature[1] are shown in Table S4.

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Table S4: Possible aldehyde products from butadiene hydroformylation and corresponding FID response factors

Entry Products

Retention

time

(experiment)

Response factor

(literature)[1]

1 2-methylbutyraldehyde 6.4 0.513

2 pentanal 7.4 0.610

3 4-pentenal 7.1 0.584

4 tran-3-pentenal 7.6 0.799

5 cis-3-pentenal 7.9 0.717

6 cyclopent-1-enecarbaldehyde 12.8 0.739

7 2-ethylbutadial 14.0 0.506

8 2-methylpentadial 14.4 0.557

9 adipaldehyde 15.4 0.321

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D. Turnover frequency calculation

Fig. S3. Temporal syngas consumption (a) and products concentrantion (b) profiles for

hydroformylation of butadiene catalyzed by (CO)2Rh(acac) with DIOP. Reaction

conditions: 0.04 mmol (CO)2Rh(acac), molar [DIOP/Rh] ratio = 3, syngas pressure = 14

bar; molar [H2/CO] ratio = 1, 15 mL toluene, 80 C, 260 min, 1000 rpm.

The linear portion of the syngas consumption profile is used as guidance for

determining the approximate time till which the slope of the rate curve is nearly linear.

For example, in Fig. S3, the syngas consumption is approximately 4 mmol and occurs at

approximately 20 minutes. Based on this, the TOF was estimated based on summing the

concentration of products at 20 minutes.

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E. Reaction parameter effects on butadiene hydroformylation

Fig. S4. Syngas consumption profiles for hydroformylation of butadiene catalyzed by

(CO)2Rh(acac) with DIOP. Reaction conditions: 0.04 mmol (CO)2Rh(acac), 15 mL

toluene, 80 C, 260 min, 1000 rpm. Entries in the legend correspond to Table 1.

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2-methylbutyraldehyde 4-pentenal pentanal trans-3-pentenal

cis-3-pentenal 2-ethylbutanedial 2-methylpentanedial adipaldehyde

Fig. S5. Temporal selectivity profiles for hydroformylation of butadiene catalyzed by

rhodium with ligand DIOP at various reaction conditions corresponding to Table 1.

Reaction conditions: 5.7 mmol butadiene, 0.04 mmol (CO)2Rh(acac), molar [H2/CO]

ratio = 1, 15 mL toluene, 80 C, 260 min, 1000 rpm.

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F. Ligand effect on butadiene and 4-pentenal hydroformylation

DPPE DPPP DPPB DPPF

DIOP 6-DPPon Xantphos Biphephos

Fig. S6. Syngas consumption profiles for hydroformylation of butadiene (a) and 4-

pentenal (b) catalyzed by rhodium with ligand DPPE, DPPP, DPPB, DPPF, DIOP, 6-

DPPon, Xantphos and Biphephos. Reaction condition for butadiene hydroformylation:

5.7 mmol butadiene, 0.04 mmol (CO)2Rh(acac), molar [P/Rh] ratio = 6, syngas pressure

= 14 bar; molar [H2/CO] ratio = 1, 15 mL toluene, 80 C, 260 min, 1000 rpm. Reaction

condition for 4-pentenal hydroformylation: 2 mmol 4-pentenal, 0.02 mmol

(CO)2Rh(acac), molar [P/Rh] ratio = 6, syngas pressure = 14 bar; molar [H2/CO] ratio =

1, 15 mL toluene, 80 C, 80 min, 1000 rpm.

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2-methylbutyraldehyde 4-pentenal pentanal trans-3-pentenal

cis-3-pentenal 2-ethylbutanedial 2-methylpentanedial adipaldehyde

Fig. S7. Temporal selectivity profiles for hydroformylation of butadiene catalyzed by

rhodium with ligand DPPE (a), DPPP (b), DPPB (c), DPPF (d), DIOP (e), 6-DPPon (f),

Xantphos (g) and Biphephos (h). Reaction conditions: 5.7 mmol butadiene, 0.04 mmol

(CO)2Rh(acac), molar [P/Rh] ratio = 6, syngas pressure = 14 bar; molar [H2/CO] ratio =

1, 15 mL toluene, 80 C, 1000 rpm.

G. ReactIR experiment

Fig. S8. Full IR spectrum and carbonyl region for butadiene hydroformylation with

DIOP/Rh.

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Fig. S9. In-situ ReactIR spectra from butadiene hydroformylation with Rh/ligand

catalysts. Rh(acac)(CO)2 and ligand dissolved in toluene at 80 as background. The IR℃

spectra of catalysts (after adding 7 bar of CO/H2 at 80 for 1 hour, blue lines) and℃

intermediates (after adding butadiene, red lines) for eight tested ligands are shown in (a)-

(h).

H. Reference

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[1] S. E. Smith, T. Rosendahl, P. Hofmann, Organometallics 30 (2011) 3643-3651.

[2] B.-C. Hong, H.-C. Tseng, S.-H. Chen, Tetrahedron 63 (2007) 2840-2850.

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