experimental supporting informationp ir-uv\inorganica\dr. juventino garcia\jorge anton 4000.0 3600...

S1

Experimental Supporting Information

Mn(I) Organometallics Containing the iPr2P(CH2)2PiPr2 Ligand

for the Catalytic Hydration of Aromatic Nitriles

Jorge A. Garduño, Alma Arévalo, Marcos Flores-Alamo and Juventino J. Garcia*

Facultad de Química, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico.

Index by categories

Experimental procedures

Procedure S1. Assays of air-stability for 1 ................................................................................... S7 Procedure S2. Competence for a vacant site in the “fac-[(CO)3Mn(dippe)]” core ..................... S15 Procedure S3. Thermolysis of 4 in a 1:2 v/v mixture of THF-d8/H2O ........................................ S17 Procedure S4. 31P{1H} NMR analysis of the binding of benzamide to the “fac-

[(CO)3Mn(dippe)]+” core .................................................................................................... S18 Procedure S5. 31P{1H} NMR analysis of the model reaction crude. .......................................... S19 Procedure S6. NMR analysis of the addition of water to a mixture of 2 and excess benzonitrile.

............................................................................................................................................. S20 Procedure S7. NMR monitoring of the actual model reaction mixture. ..................................... S21 Procedure S8. Single crystal X-Ray Diffraction for 2 ................................................................ S23 Procedure S9. General procedure for the catalytic hydration of nitriles with complex 2 ........... S29

Figures Figure S1. 1H NMR (300 MHz, THF-d8) spectrum of 1. ............................................................. S4 Figure S2. 31P{1H} NMR (121 MHz, THF-d8) spectrum of 1. ..................................................... S5 Figure S3. FTIR (ATR) spectrum of 1. ......................................................................................... S6 Figure S4. 31P{1H} NMR (121 MHz) analysis of a CDCl3 solution of 1 exposed to air. ............. S7 Figure S5. 1H NMR (300 MHz) of a CDCl3 solution of 1 exposed to air for one week. ............. S7 Figure S6. 1H NMR (300 MHz, THF-d8) spectrum of 2 .............................................................. S8 Figure S7. 31P{1H} NMR (121 MHz, THF-d8) spectrum of 2. ..................................................... S9 Figure S8. 19F NMR (282 MHz, THF-d8) spectrum of 2. ............................................................. S9 Figure S9. FTIR (ATR) spectrum of 2. ....................................................................................... S10 Figure S10. 1H NMR (300 MHz, THF-d8) spectrum of 3. ......................................................... S11 Figure S11. 31P{1H} NMR (121 MHz, THF-d8) spectrum of 3. ................................................. S12 Figure S12. 19F NMR (282 MHz, THF-d8) spectrum of 3. ......................................................... S12 Figure S13. FTIR (ATR) spectrum of 3. ..................................................................................... S13 Figure S14. 1H NMR (300 MHz, C7D8) spectrum of 3. ............................................................. S14 Figure S15. 31P{1H} NMR (121 MHz, C7D8) spectrum of 3. ..................................................... S14 Figure S16. 1H NMR (300 MHz) spectra for 3 in THF-d8 solution and with added PhCN. ...... S15

Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2018

S2

Figure S17. 31P{1H} NMR (121 MHz) spectra for 3 in THF-d8 solution and with PhCN added. ............................................................................................................................................. S16

Figure S18. 1H NMR (300 MHz, THF-d8) of free and coordinated benzonitrile. ...................... S16 Figure S19. 31P{1H} NMR (121 MHz) monitoring of a THF-d8/H2O (1:2 v/v) solution of 2 at

variable temperature. ........................................................................................................... S17 Figure S20. 1H (300 MHz) spectrum of a THF-d8/H2O (1:2 v/v) solution of 2 at room

temperature. ........................................................................................................................ S18 Figure S21. 31P{1H} NMR spectra for the addition of benzamide to a THF-d8 solution of 2 .... S19 Figure S22. 31P{1H} NMR spectrum of the model reaction crude. ............................................ S20 Figure S23. 31P{1H} (162 MHz) spectra for the addition of water to a THF-d8 solution of 2 and

excess benzonitrile. ............................................................................................................. S21 Figure S24. 1H (400 MHz) spectra for the addition of water to a THF-d8 solution of 2 and excess

benzonitrile. ........................................................................................................................ S21 Figure S25. 31P{1H} NMR (121 MHz, THF-d8) monitoring of the reaction between benzonitrile

and water catalyzed by 2. .................................................................................................... S22 Figure S26. 1H NMR (300 MHz, THF-d8) monitoring of the reaction between benzonitrile and

water catalyzed by 2. ........................................................................................................... S22 Figure S27. ORTEP plot (50% probability, 130 K) for complex 2 ............................................ S29 Figure S28. 1H NMR (400 MHz, DMSO-d6) aromatic region of the spectrum of isolated

benzamide from optimized model reaction ......................................................................... S30 Figure S29. 1H NMR (400 MHz, DMSO-d6) spectrum of isolated benzamide from optimized

model reaction ..................................................................................................................... S31 Figure S30. 13C{1H} NMR (100 MHz, DMSO-d6) spectrum of isolated benzamide from

optimized model reaction .................................................................................................... S31 Figure S31. MS(EI) of isolated benzamide from optimized model reaction .............................. S32 Figure S32. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

trifluoromethylbenzamide ................................................................................................... S32 Figure S33. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

trifluoromethylbenzamide ................................................................................................... S33 Figure S34. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

trifluoromethylbenzamide ................................................................................................... S33 Figure S35. MS(EI) of p-trifluoromethylbenzamide .................................................................. S34 Figure S36. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-fluorobenzamide . S34 Figure S37. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

fluorobenzamide ................................................................................................................. S35 Figure S38. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated p-fluorobenzamide S35 Figure S39. MS(EI) of p-fluorobenzamide ................................................................................. S36 Figure S40. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-

pentafluorobenzamide ......................................................................................................... S36 Figure S41. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-

pentafluorobenzamide ......................................................................................................... S37 Figure S42. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-

pentafluorobenzamide ......................................................................................................... S37 Figure S43. MS(EI) of 2,3,4,5,6-pentafluorobenzamide ............................................................ S38 Figure S44. MS(EI) of isonicotinamide ...................................................................................... S38 Figure S45. MS(EI) of nicotinamide .......................................................................................... S39

S3

Figure S46. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated picolinamide .......... S39 Figure S47. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated picolinamide . S40 Figure S48. MS(EI) of picolinamide .......................................................................................... S40 Figure S49. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-methoxybenzamide

............................................................................................................................................. S41 Figure S50. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

methoxybenzamide ............................................................................................................. S41 Figure S51. MS(EI) of p-methoxybenzamide ............................................................................. S42 Figure S52. MS(EI) of p-toluamide ............................................................................................ S42 Figure S53. 1H NMR (400 MHz, DMSO-d6) spectrum of isolated furan-2-carbamide ............. S43 Figure S54. 13C{1H} NMR (100 MHz, DMSO-d6) spectrum of isolated furan-2-carbamide .... S43 Figure S55. MS(EI) of furan-2-carbamide .................................................................................. S44

Tables

Table S1. Crystal data and structure refinement for 2. ............................................................... S23 Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x

103) for 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ..... S24 Table S3. Bond lengths [Å] and angles [°] for 2. ........................................................................ S25 Table S4. Torsion angles [°] for 2. .............................................................................................. S28

S4

Characterization of fac-[(CO)3Mn(dippe)(Br)] (1)

1 (146.2 mg, 84%). 1H NMR (300 MHz, THF-d8, δ/ ppm) 3.58 (s, THF), 2.90-2.69 (m, 1H), 2.38-2.22 (m, 1H), 2.18-1.88 (m, 2H), 1.73 (s, THF), 1.47-1.16 (m, 12H). 31P{1H} NMR (121 MHz, THF-d8, δ/ ppm) 80.45 (s). FTIR (ATR) νC-H (cm-1) 2960.77 m, 2934.09 w, 2898.91 w, 2874.40 w; νC-O (cm-1) 2001.29 s, 1921.98 s, 1885.76 s. Anal. Calcd for 1, C17H32BrMnO3P2: C, 42.43; H, 6.70. Found: C, 42.46; H, 6.83.

Figure S1. 1H NMR (300 MHz, THF-d8) spectrum of 1.

-0.20.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.8f1 (ppm)

1H-JGR-d001-THF-d8-18-08-2016JGR-d0011H 300 MHzTHF-d818-08-2016JAGR

1.0

0

1.0

4

2.0

7

13

.37

0.1

0

1.2

31.2

81.3

11.3

41.3

61.3

81.4

11.4

6

1.7

31.8

81.9

71.9

82.0

12.0

32.0

82.1

02.1

22.1

82.2

22.2

92.3

02.3

82.7

12.7

52.7

72.7

92.8

02.8

22.8

42.8

42.8

9

3.5

8

MnCOP

Br

CO

COP

iPriPr

iPriPr

1

S5

Figure S2. 31P{1H} NMR (121 MHz, THF-d8) spectrum of 1.

0102030405060708090100110120130140150f1 (ppm)

31P-JGR-d001-THF-d8-18-08-2016JGR-d00131P 121.4 MHzTHF-d818-08-2016JAGR

80.4

5

MnCOP

Br

CO

COP

iPriPr

iPriPr

1

S6

Figure S3. FTIR (ATR) spectrum of 1.

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S7

Procedure S1. Assays of air-stability for 1

1 (5 mg) was exposed to air in the solid state, dissolved in CDCl3 (0.5 mL) and placed into an NMR tube. This solution was monitored both after 20 min and one week. Recorded spectra are as follows:

Figure S4. 31P{1H} NMR (121 MHz) analysis of a CDCl3 solution of 1 exposed to air.

Figure S5. 1H NMR (300 MHz) of a CDCl3 solution of 1 exposed to air for one week.

0102030405060708090100110f1 (ppm)

CDCl3 solution of 1 exposed to air for one week

80.2 ppm

80.2 ppm

80.5 ppm

CDCl3 solution of 1 exposed to air for 20 min

THF-d8 solution of 1 under an inert atmosphere

0.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.1f1 (ppm)

1H-JGR-d001-CDCl3-31-08-2016JGR-d0011H 300 MHzCDCl331-08-2016JAGR

1.0

0

1.0

9

2.2

0

11

.79

1.2

81.3

11.3

31.3

51.3

71.4

01.4

01.4

3

1.7

61.7

81.8

01.8

41.8

71.9

01.9

21.9

41.9

51.9

72.0

02.0

32.0

82.1

02.1

72.2

12.2

32.2

52.2

82.3

02.3

22.3

5

2.7

32.7

62.7

82.8

12.8

32.8

6

S8

Characterization of for fac-[(CO)3Mn(dippe)(OSO2CF3)] (2)

2 (43.4 mg, 75%). 1H NMR (300 MHz, THF-d8, δ/ ppm) 2.53-2.27 (m, 1H), 2.18-2.00 (m, 1H), 1.47-1.30 (m, 6H). 31P{1H} NMR (121 MHz, THF-d8, δ/ ppm) 85.74 (s). 19F NMR (282 MHz, THF-d8, δ/ ppm) -78.19 (s). FTIR (ATR) νC-H (cm-1) 2968.39 m, 2941.35 w, 2881.54 w; νC-O (cm-1) 2021.57 s, 1957.71 s, 1895.22 s. Anal. Calcd for 2, C18H32F3MnO6P2S: C, 39.28; H, 5.86; S, 5.82. Found: C, 38.44; H, 5.88; S, 5.75.

Figure S6. 1H NMR (300 MHz, THF-d8) spectrum of 2

0.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.73.8f1 (ppm)

JGR-d004.10.fid

1.0

0

0.9

6

5.7

2

0.8

70.8

90.9

60.9

8

1.3

01.3

11.3

21.3

41.3

51.3

61.3

71.3

91.4

01.4

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41.4

7

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31.9

72.0

02.0

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92.1

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82.5

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MnCO

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PCO

COP

iPr iPr

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O

CF3

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S9


Figure S8. 19F NMR (282 MHz, THF-d8) spectrum of 2.

0102030405060708090100110120130140150f1 (ppm)

JGR-d004.11.fid

85

.74

-78.95-78.90-78.85-78.80-78.75-78.70-78.65-78.60-78.55-78.50-78.45-78.40-78.35-78.30-78.25-78.20-78.15-78.10-78.05-78.00-77.95-77.90-77.85-77.80-77.75-77.70-77.65-77.60f1 (ppm)

JGR-d004.12.fid

-7

8.8

8

-7

8.6

7

-7

8.4

2

-7

8.3

6

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MnCO

O

PCO

COP

iPr iPr

iPriPr S

O

CF3

O2

MnCO

O

PCO

COP

iPr iPr

iPriPr S

O

CF3

O2

S10


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19

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12

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8

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S11

Characterization of fac-[(CO)3Mn(dippe)(κ1-PhCN)](OSO2CF3) (3)

3 (30.9 mg, 85%). 1H NMR (300 MHz, THF-d8, δ/ ppm) 8.06-7.49 (m, 5H), 3.58 (s, THF), 2.78-1.94 (m, 8H), 1.73 (s, THF), 1.53-1.23 (m, 24 H). 31P{1H} NMR (121 MHz, THF-d8, δ/ ppm) 3, 87.03 (s); 2, 85.74 (s). 19F NMR (282 MHz, THF-d8, δ/ ppm) -78.17. FTIR (ATR) νC-H (cm-1) 2965.79 w, 2939.65 w, 2878.40 w, 2903.02 w; νC-N (cm-1) 2250.91 vw; νC-O (cm-1) 2021.53 s, 1937.65 s, 1921.16 s. Anal. Calcd for 3, C25H37F3MnNO6P2S: C, 45.95; H, 5.71; N, 2.14; S, 4.91. Found: C, 44.06; H, 5.77; N, 2.00; S, 5.03.

Figure S10. 1H NMR (300 MHz, THF-d8) spectrum of 3.

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

JGR-d006-.10.fid

1.0

0 1.7

3

5.0

1

0.1

10.8

40.8

60.8

90.9

10.9

60.9

81.3

11.3

21.3

31.3

41.3

61.3

81.3

91.4

21.4

51.4

71.4

71.5

01.7

32.0

22.0

42.0

52.0

72.0

82.0

92.1

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92.3

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62.4

82.5

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92.6

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82.6

92.7

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97.5

17.5

37.5

67.5

87.6

17.6

37.6

67.6

97.7

07.7

17.7

27.7

58.0

38.0

6

MnCOP

N

CO

COP

iPriPr

iPriPr

3

OSO2CF3

S12


Figure S12. 19F NMR (282 MHz, THF-d8) spectrum of 3.

0102030405060708090100110120130140150f1 (ppm)

JGR-d006-.12.fid

85

.74

87

.03

-79.6-79.5-79.4-79.3-79.2-79.1-79.0-78.9-78.8-78.7-78.6-78.5-78.4-78.3-78.2-78.1-78.0-77.9-77.8-77.7-77.6-77.5-77.4-77.3-77.2-77.1-77.0-76.9f1 (ppm)

JGR-d006-.13.fid

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8.8

7

-7

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COP

iPriPr

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OSO2CF3

MnCOP

N

CO

COP

iPriPr

iPriPr

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OSO2CF3

S13


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28

.46

92

6.1

1

88

2.0

9 81

3.7

07

59

.79

70

4.9

8

68

9.6

6

68

3.3

2

66

8.4

56

58

.57

63

3.9

0

61

0.4

1

57

1.0

0

55

6.9

5

54

5.4

15

26

.61

51

5.3

7

48

8.4

6

46

8.6

3

MnCOP

N

CO

COP

iPriPr

iPriPr

3

OSO2CF3

S14

Figure S14. 1H NMR (300 MHz, C7D8) spectrum of 3.

Figure S15. 31P{1H} NMR (121 MHz, C7D8) spectrum of 3.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

JGR-d006B.11.fid

0.2

60.8

20.8

40.8

80.9

40.9

60.9

91.0

81.1

11.2

81.3

01.3

21.3

71.4

12.0

72.0

72.0

82.0

92.0

92.4

3

2.7

7

6.6

66.6

96.7

16.8

16.8

46.8

66.9

77.0

17.0

9

7.7

0

404550556065707580859095100105110115120125130135f1 (ppm)

JGR-d006B.13.fid

85.2

3

86.8

7

MnCOP

N

CO

COP

iPriPr

iPriPr

3

OSO2CF3

MnCOP

N

CO

COP

iPriPr

iPriPr

3

OSO2CF3

S15

Procedure S2. Competence for a vacant site in the “fac-[(CO)3Mn(dippe)]” core

In the glovebox, 3 (11 mg, 0.017 mmol) was dissolved in the minimal amount of THF-d8. To this pale-yellow solution was added a colorless THF-d8 solution of benzonitrile (5.3 mg, 0.051 mmol) to form a yellow solution, which was placed in a Wilmad NMR tube equipped with a J. Young valve and stirred for 20 minutes. An NMR analysis of this solution was performed. After that, in the glovebox, benzonitrile (29.8 mg, 0.29 mmol) was added to the same mixture and the almost colorless solution formed was stirred inside the same NMR tube for 20 minutes. A new NMR analysis of the solution was performed. Recorded spectra are as follows:

Figure S16. 1H NMR (300 MHz) spectra for 3 in THF-d8 solution and with added PhCN.

NOTE: In the figure above: (a) 3 as synthesized and purified in THF-d8 solution with no extra PhCN added; (b) 3 in THF-d8 solution with 3 equivalents of PhCN added; and (c) 3 in THF-d8 solution with 20 equivalents of PhCN added. Above each assigned signal are shown values for the integrals. In parentheses are shown the actual integral values as extracted from the spectra. From the integrals on trace (a) it is inferred some PhCN dissociates when 3 is in solution. In traces (b) and (c) the values in parentheses approximate to the expected integral values for 3, so in the presence of an excess PhCN, species 3 becomes predominant in solution.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

JGR-d019-2.10.fid

JGR-d019-.10.fid

JGR-d006-.10.fid

(a) 3 in THF-d8

(b) 3 + 3 PhCN

(c) 3 + 20 PhCN

2H (1.00) 8H (4.28)

24H (13.02)

2H (1.00) 6H (2.77)14H (6.60)

40H (19.60)

2H (1.00)

24H (13.55)

8H (4.54)

S16

Figure S17. 31P{1H} NMR (121 MHz) spectra for 3 in THF-d8 solution and with PhCN added.

NOTE: In Figure S17: (a) 3 as synthesized and purified in THF-d8 solution with no extra PhCN added; (b) 3 in THF-d8 solution with 3 equivalents of PhCN added; and (c) 3 in THF-d8 solution with 20 equivalents of PhCN added. Signals are assigned to species 2 (86 ppm) and 3 (87 ppm) coexisting in solution in trace (a). On increasing the concentration of PhCN [traces (b) and (c)], species 3 becomes predominant.

Figure S18. 1H NMR (300 MHz, THF-d8) of free and coordinated benzonitrile.

NOTE: In Figure S18: the green trace displays the signals for free benzonitrile and the blue trace corresponds to a mixture of free and coordinated benzonitrile in complex 3. Blue trace was taken from the aromatic region of trace b in Figure S16.

(a) 3 in THF-d8 solution

5101520253035404550556065707580859095100105110115120125130f1 (ppm)

(b) 3 + 3 PhCN

(c) 3 + 20 PhCN

3 (87 ppm)

3 (87 ppm)

3 (87 ppm)

2 (86 ppm)

2 (86 ppm)

7.457.507.557.607.657.707.757.807.857.907.958.008.058.10f1 (ppm)

7.4

9

7.5

1

7.5

4

7.5

6

7.5

8

7.6

1

7.6

3

7.6

6

7.6

9

7.7

2

7.7

5

8.0

4

8.0

7

S17

Procedure S3. Thermolysis of 4 in a 1:2 v/v mixture of THF-d8/H2O

In a Wilmad NMR tube equipped with a J. Young valve, 2 (5 mg, 0.0092 mmol) was dissolved in THF-d8 (0.5 mL) and then H2O (1 mL, 0.055 mmol) was added. The readily formed yellow solution was heated in an oil bath at 100 ºC for 6 h and then for 12 h to complete a total heating time of 18 h. 31P{1H} NMR analysis of the mixture at t = 0, 6 h, and 18 h, were performed at room temperature. Recorded spectra are as follows:

Figure S19. 31P{1H} NMR (121 MHz) monitoring of a THF-d8/H2O (1:2 v/v) solution of 2 at variable

temperature.

NOTE: Upon the addition of excess water to a THF-d8 solution of 2, the corresponding chemical shift changes from δP 85.7 ppm (See Figure S7) to δP 86.8. On the basis of the observed phenomena when increasing the amount of a neutral donor molecule in the medium, namely benzonitrile (See Figure S17), the new signal at 86.8 ppm is proposed to stem from species fac-[(CO)3Mn(dippe)(OH2)](OTf) (4).

-100-90-80-70-60-50-40-30-20-100102030405060708090100110120130f1 (ppm)

THF-d8/H2O (1:2) solution of 2 at room temperature

THF-d8/H2O (1:2) solution of 2 heated at 100 ºC for 6 h

THF-d8/H2O (1:2) solution of 2 heated at 100 ºC for 18 h

86.8 ppm

86.8 ppm

86.8 ppm

16 ppm18 ppm

S18

Figure S20. 1H (300 MHz) spectrum of a THF-d8/H2O (1:2 v/v) solution of 2 at room temperature.

Procedure S4. 31P{1H} NMR analysis of the binding of benzamide to the “fac-[(CO)3Mn(dippe)]+” core

In the glovebox, 2 (15 mg, 0.027 mmol) was dissolved in the minimal amount of THF-d8. To this yellow solution was added a colorless THF-d8 solution of benzamide (3.3 mg, 0.027 mmol) to form a yellow solution, which was placed in a Wilmad NMR tube equipped with a J. Young valve and stirred for 20 minutes. An NMR analysis of this solution was performed. After that, in the glovebox, to the same mixture was added benzamide (29 mg, 0.24 mmol) and the yellow solution formed was stirred inside the same NMR tube for 20 minutes. A new NMR analysis of the solution was performed. Recorded spectra are as follows:

-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

JGRd035.10.fid

1.2

6

1.7

3

2.1

3

2.4

8

3.6

0

4.5

6

1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.7f1 (ppm)

1.1

81.2

01.2

41.2

51.2

61.2

71.3

01.3

11.3

21.3

41.3

61.3

9

1.7

3

2.0

42.0

52.0

82.1

02.1

32.1

52.1

62.4

32.4

42.4

62.4

72.4

82.4

92.5

02.5

12.5

32.5

42.5

52.5

6

H2O

MnCO

OH2

PCO

COP

iPr iPr

iPriPr

4

OSO2CF3

S19

Figure S21. 31P{1H} NMR spectra for the addition of benzamide to a THF-d8 solution of 2

NOTE: Upon the addition of excess benzamide to a THF-d8 solution of 2, a new signal is observed at δP 87.8. On the basis of the observed phenomena when increasing the amount of a neutral donor molecule in the medium, namely benzonitrile (See Figure S17), new signal at 87.8 ppm is proposed to stem from species fac-[(CO)3Mn(dippe)(PhC(O)NH2)](OTf) (5).

Procedure S5. 31P{1H} NMR analysis of the model reaction crude.

In the glovebox, a colorless THF solution of benzonitrile (47.3 mg, 0.46 mmol) was added dropwise to a yellow THF solution of 2 (5 mg, 0.0092 mmol). The readily formed yellow solution was transferred to a 25 mL Schlenk tube (Synthware Glass) (1 mL THF total volume), to which water (2 mL, 111 mmol) was added to form a pale-yellow emulsion. The reaction mixture was stirred into an oil bath at 100 ºC during 18 h. After that, the solvent and volatiles were removed under reduced pressure in the inert gas/ vacuum double manifold and the residue was dried under vacuum for 4 h. Taking care to not expose the remaining mixture to the air, this was dissolved in THF-d8 inside the glovebox and transferred to a Wilmad NMR tube equipped with a J. Young valve to perform the corresponding analysis of the readily formed yellow solution.

-10-505101520253035404550556065707580859095100105110115120125130f1 (ppm)

1175-31P_JGRD051A31P H3PO4 / D2O0 ppm05.junio.2017tpwr=53 pw90=8

1143-31P_JGRD0511143

USAII-UNAM21.JUNIO.2017Dr. Juventino GarciaJorge GarduÃ±o / THF-d831p 162 MHz400-VNMRSRDM

(a) THF-d8 solution of 2 with 1 equivalent of benzamide added

(b) THF-d8 solution of 2 with 10 equivalents of benzamide added

2 (85.7 ppm)

5 (87.8 ppm)

5 (87.8 ppm)

2 (85.7 ppm)

S20

Figure S22. 31P{1H} NMR spectrum of the model reaction crude.

NOTE: In the (e) trace is displayed the spectrum recorded after performing the experiment described in

Procedure S5. The (a) to (d) upper traces are included for comparative purposes.

Procedure S6. NMR analysis of the addition of water to a mixture of 2 and excess benzonitrile.

In the glovebox, 2 (20.4 mg, 0.037 mmol) was dissolved in the minimal amount of THF-d8. To this yellow solution was added a colorless THF-d8 solution of benzonitrile (192 mg, 1.86 mmol) to form a yellow solution, which was placed in a Wilmad NMR tube equipped with a J. Young valve and stirred for 20 minutes to finally yield a pale-yellow solution. An NMR analysis of this solution was performed. After that, in the glovebox, to the same mixture was added water (1 µL, 0.056 mmol) and the yellow solution formed was stirred inside the same NMR tube for 20 minutes. A new NMR analysis of the solution was performed. Finally, in the glovebox, to the same mixture was added water (32 µL, 1.78 mmol) and the yellow solution formed was stirred inside the same NMR tube for 20 minutes. A final NMR analysis of the solution was performed. Recorded spectra are as follows:

5101520253035404550556065707580859095f1 (ppm)

(2)

(3)

(2)

(4)

(2)

(4)

(5)

(2)(5)

(dippe)

chemical shift

(2): fac-[(CO)3Mn(dippe)(OTf)] 85.7 ppm

(3): fac-[(CO)3Mn(dippe)(PhCN)](OTf) 87.0 ppm

(4): fac-[(CO)3Mn(dippe)(H2O)](OTf) 86.8 ppm

(5): fac-[(CO)3Mn(dippe)(PhC(O)NH2)](OTf) 87.8 ppm

dippe 9.2 ppm

(a)

(b)

(c)

(d)

(e)

THF-d8 solution of "as synthesized" 3

THF-d8 solution of 2

THF-d8/H2O (1:2 v/v) solution of 2 heated at 100 ºC for 18 h

THF-d8 solution of 2 with 10 equivalents of benzamide added

THF-d8 solution of the reaction crude

Conditions: A THF/H2O (1:2 v/v) solution of 2 with added PhCN (50 equiv.) heated at 100 ºC for 18 h

S21

Figure S23. 31P{1H} (162 MHz) spectra for the addition of water to a THF-d8 solution of 2 and

excess benzonitrile.

Figure S24. 1H (400 MHz) spectra for the addition of water to a THF-d8 solution of 2 and excess

benzonitrile.

NOTE: In the 1H NMR spectra, upon the addition of water [0 equiv (red trace), 1.5 equiv (green trace), and 50 equiv (blue trace)] to a THF-d8 solution of 2 and 50 equiv of benzonitrile, the signature signal for coordinated benzonitrile shown in the inset is still observed (to compare see Figure S18). Additionally, in the 31P{1H} spectra only one signal is observed, corresponding to complex 3, indicating that under these conditions water does not substitute benzonitrile at the [Mn] core. Procedure S7. NMR monitoring of the actual model reaction mixture.

In the glovebox, a THF-d8 colorless solution of benzonitrile (47.3 mg, 0.46 mmol) was added dropwise to a yellow THF-d8 solution of 2 (5 mg, 0.0092 mmol). The readily formed yellow solution was transferred to a Wilmad NMR tube equipped with a J. Young valve (0.6 mL THF total volume), to which water (1 mL, 56 mmol) was added to form a pale-yellow emulsion. An NMR analysis of the as prepared mixture (aqueous layer) was performed at room temperature. Then, the reaction mixture was heated into an oil bath at 100 ºC for 3 h during which a pale-yellow solution was observed inside the NMR tube. After that, acquisition of NMR spectra was performed at room temperature. Finally, the reaction mixture was heated

-200-180-160-140-120-100-80-60-40-20020406080100120140160180200f1 (ppm)

2 + 50 PhCN in THF-d8 at room temperature

2 + 50 PhCN + 1.5 H2O in THF-d8 at room temperature

2 + 50 PhCN + 50 H2O in THF-d8 at room temperature

7.407.457.507.557.607.657.707.757.807.857.907.958.008.058.10f1 (ppm)

7.867.887.907.927.947.967.988.008.028.04f1 (ppm)

S22

into an oil bath at 100 ºC during 6 h (accumulated time of 9 h) and new NMR spectra were recorded at room temperature.

Figure S25. 31P{1H} NMR (121 MHz, THF-d8) monitoring of the reaction between benzonitrile and

water catalyzed by 2.

Figure S26. 1H NMR (300 MHz, THF-d8) monitoring of the reaction between benzonitrile and water catalyzed by 2.

3035404550556065707580859095100105110115120125130135140f1 (ppm)

(a)

(b)

(c)

As prepared model reaction mixture

Model reaction mixture after 3 h at 100 ºC


86.6 ppm

86.6 ppm

86.6 ppm

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

(a)

(b)

(c)

As prepared model reaction mixture



S23

Procedure S8. Single crystal X-Ray Diffraction for 2

In the glovebox, a freshly synthesized batch of 2 (20 mg, 0.036 mmol) was dissolved in toluene (about 1 mL). The yellow solution was stored at -30 ºC for 48 h under an argon atmosphere, after which yellow crystals were obtained. Before analysis, the solid was protected with Fluorolube®.

Table S1. Crystal data and structure refinement for 2.

Identification code 2 Empirical formula C18 H32 F3 Mn O6 P2 S Formula weight 550.37 Temperature 130(2) K Wavelength 0.71073 Å Crystal system Orthorhombic Space group P 21 21 21 Unit cell dimensions a = 8.6949(6) Å b = 13.9549(9) Å c = 19.9508(15) Å Volume 2420.8(3) Å3 Z 4 Density (calculated) 1.510 Mg/m3 Absorption coefficient 0.818 mm-1 F(000) 1144 Crystal size 0.400 x 0.130 x 0.030 mm3 Theta range for data collection 3.394 to 25.347°. Index ranges -6

S24

Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

x x y z U(eq) C(1) 3651(13) 5646(10) 6474(7) 40(3) C(2) 3487(16) 5518(11) 5757(8) 63(4) C(3) 4850(20) 4921(12) 4492(9) 75(3) C(4) 5077(18) 5826(12) 4132(7) 70(4) C(6) 5040(20) 3671(12) 5702(9) 75(3) C(9) 5891(14) 5534(8) 7506(6) 36(3) C(10) 7459(15) 5787(9) 7817(6) 45(3) C(11) 4598(16) 5688(10) 8003(6) 50(3) C(12) 5174(15) 7399(7) 6881(6) 36(3) C(13) 6649(15) 7980(9) 6965(7) 49(4) C(14) 4131(16) 7876(9) 6365(6) 45(3) C(15) 8923(17) 6372(9) 6206(6) 38(3) C(16) 6870(14) 6760(10) 5372(7) 43(3) C(17) 8454(15) 5320(8) 5120(6) 35(3) C(18) 8930(17) 3053(10) 6998(8) 50(4) F(1) 7809(11) 2530(6) 6743(6) 92(3) F(2) 10145(10) 2511(5) 7067(4) 68(3) F(3) 8502(12) 3341(7) 7585(5) 84(3) Mn(1) 7299(2) 5720(1) 5830(1) 30(1) O(6) 9120(12) 5135(7) 4653(5) 56(3) O(1) 9961(10) 6820(6) 6377(4) 44(2) O(2) 6706(11) 7483(6) 5092(5) 49(2) O(3) 7815(9) 4497(5) 6404(4) 33(2) O(4) 9857(13) 3663(7) 5858(5) 68(3) O(5) 10440(11) 4614(6) 6842(5) 59(3) P(1) 5165(4) 4897(2) 5393(2) 34(1) P(2) 5562(4) 6123(2) 6686(2) 31(1) S(1) 9350(4) 4064(2) 6454(2) 36(1) C(5) 3420(20) 4412(17) 4268(12) 75(3) C(7) 6120(50) 3080(20) 5240(20) 75(3) C(8) 3500(30) 3263(18) 5859(15) 75(3) C(5P) 2890(50) 5100(60) 4560(40) 75(3) C(7P) 5890(90) 2930(40) 5350(40) 75(3) C(8P) 4400(60) 3430(40) 6340(20) 75(3)

S25

Table S3. Bond lengths [Å] and angles [°] for 2.

C(1)-C(2) 1.447(19) C(1)-P(2) 1.840(12) C(1)-H(1A) 1.0078 C(1)-H(1B) 0.9900 C(2)-P(1) 1.846(15) C(2)-H(2A) 0.9105 C(2)-H(2B) 0.9734 C(3)-C(4) 1.47(2) C(3)-C(5) 1.50(2) C(3)-C(5P) 1.73(4) C(3)-P(1) 1.817(18) C(3)-H(3) 1.0000 C(4)-H(4A) 0.9800 C(4)-H(4B) 0.9800 C(4)-H(4C) 0.9800 C(6)-C(8P) 1.43(4) C(6)-C(7P) 1.46(5) C(6)-C(8) 1.49(3) C(6)-C(7) 1.55(4) C(6)-P(1) 1.822(17) C(6)-H(6) 1.0134 C(9)-C(11) 1.514(16) C(9)-C(10) 1.539(17) C(9)-P(2) 1.854(11) C(9)-H(9) 1.0000 C(10)-H(10A) 0.9800 C(10)-H(10B) 0.9800 C(10)-H(10C) 0.9800 C(11)-H(11A) 0.9800 C(11)-H(11B) 0.9800 C(11)-H(11C) 0.9800 C(12)-C(14) 1.525(16) C(12)-C(13) 1.527(17) C(12)-P(2) 1.853(11) C(12)-H(12) 1.0000 C(13)-H(13A) 0.9800 C(13)-H(13B) 0.9800 C(13)-H(13C) 0.9800 C(14)-H(14A) 0.9800 C(14)-H(14B) 0.9800 C(14)-H(14C) 0.9800 C(15)-O(1) 1.150(15) C(15)-Mn(1) 1.840(15) C(16)-O(2) 1.163(15) C(16)-Mn(1) 1.756(14) C(17)-O(6) 1.125(14) C(17)-Mn(1) 1.825(13) C(18)-F(3) 1.293(17) C(18)-F(2) 1.306(15) C(18)-F(1) 1.320(16) C(18)-S(1) 1.817(14) Mn(1)-O(3) 2.103(7)

Mn(1)-P(2) 2.348(4) Mn(1)-P(1) 2.350(4) O(3)-S(1) 1.468(8) O(4)-S(1) 1.385(10) O(5)-S(1) 1.445(9) C(5)-H(5A) 0.9800 C(5)-H(5B) 0.9800 C(5)-H(5C) 0.9800 C(7)-H(7A) 0.9800 C(7)-H(7B) 0.9800 C(7)-H(7C) 0.9800 C(8)-H(8A) 0.9800 C(8)-H(8B) 0.9800 C(8)-H(8C) 0.9800 C(5P)-H(5PA) 0.9800 C(5P)-H(5PB) 0.9800 C(5P)-H(5PC) 0.9800 C(7P)-H(7PA) 0.9800 C(7P)-H(7PB) 0.9800 C(7P)-H(7PC) 0.9800 C(8P)-H(8PA) 1.0473 C(8P)-H(8PB) 0.9800 C(8P)-H(8PC) 0.9801 C(2)-C(1)-P(2) 111.2(9) C(2)-C(1)-H(1A) 133.4 P(2)-C(1)-H(1A) 99.1 C(2)-C(1)-H(1B) 109.3 P(2)-C(1)-H(1B) 109.3 H(1A)-C(1)-H(1B) 91.9 C(1)-C(2)-P(1) 111.6(10) C(1)-C(2)-H(2A) 96.6 P(1)-C(2)-H(2A) 113.6 C(1)-C(2)-H(2B) 97.9 P(1)-C(2)-H(2B) 114.5 H(2A)-C(2)-H(2B) 119.3 C(4)-C(3)-C(5) 111.9(16) C(4)-C(3)-C(5P) 93(3) C(4)-C(3)-P(1) 118.7(12) C(5)-C(3)-P(1) 114.2(14) C(5P)-C(3)-P(1) 94(3) C(4)-C(3)-H(3) 103.1 C(5)-C(3)-H(3) 103.2 C(5P)-C(3)-H(3) 146.5 P(1)-C(3)-H(3) 103.3 C(3)-C(4)-H(4A) 109.5 C(3)-C(4)-H(4B) 109.5 H(4A)-C(4)-H(4B) 109.5 C(3)-C(4)-H(4C) 109.5 H(4A)-C(4)-H(4C) 109.5 H(4B)-C(4)-H(4C) 109.5 C(8P)-C(6)-C(7P) 117(3)

S26

C(8)-C(6)-C(7) 118(2) C(8P)-C(6)-P(1) 123(2) C(7P)-C(6)-P(1) 118(3) C(8)-C(6)-P(1) 118.9(15) C(7)-C(6)-P(1) 105.2(15) C(8P)-C(6)-H(6) 85.3 C(7P)-C(6)-H(6) 92.6 C(8)-C(6)-H(6) 136.4 C(7)-C(6)-H(6) 88.3 P(1)-C(6)-H(6) 82.2 C(11)-C(9)-C(10) 111.2(10) C(11)-C(9)-P(2) 113.6(8) C(10)-C(9)-P(2) 113.0(8) C(11)-C(9)-H(9) 106.1 C(10)-C(9)-H(9) 106.1 P(2)-C(9)-H(9) 106.1 C(9)-C(10)-H(10A) 109.5 C(9)-C(10)-H(10B) 109.5 H(10A)-C(10)-H(10B) 109.5 C(9)-C(10)-H(10C) 109.5 H(10A)-C(10)-H(10C) 109.5 H(10B)-C(10)-H(10C) 109.5 C(9)-C(11)-H(11A) 109.5 C(9)-C(11)-H(11B) 109.5 H(11A)-C(11)-H(11B) 109.5 C(9)-C(11)-H(11C) 109.5 H(11A)-C(11)-H(11C) 109.5 H(11B)-C(11)-H(11C) 109.5 C(14)-C(12)-C(13) 110.0(10) C(14)-C(12)-P(2) 112.7(8) C(13)-C(12)-P(2) 112.4(8) C(14)-C(12)-H(12) 107.1 C(13)-C(12)-H(12) 107.1 P(2)-C(12)-H(12) 107.1 C(12)-C(13)-H(13A) 109.5 C(12)-C(13)-H(13B) 109.5 H(13A)-C(13)-H(13B) 109.5 C(12)-C(13)-H(13C) 109.5 H(13A)-C(13)-H(13C) 109.5 H(13B)-C(13)-H(13C) 109.5 C(12)-C(14)-H(14A) 109.5 C(12)-C(14)-H(14B) 109.5 H(14A)-C(14)-H(14B) 109.5 C(12)-C(14)-H(14C) 109.5 H(14A)-C(14)-H(14C) 109.5 H(14B)-C(14)-H(14C) 109.5 O(1)-C(15)-Mn(1) 173.0(11) O(2)-C(16)-Mn(1) 173.8(11) O(6)-C(17)-Mn(1) 174.4(11) F(3)-C(18)-F(2) 108.5(12) F(3)-C(18)-F(1) 108.0(14) F(2)-C(18)-F(1) 108.5(12) F(3)-C(18)-S(1) 111.0(10) F(2)-C(18)-S(1) 110.5(11) F(1)-C(18)-S(1) 110.3(10) C(16)-Mn(1)-C(17) 88.0(5)

C(16)-Mn(1)-C(15) 88.1(5) C(17)-Mn(1)-C(15) 92.6(6) C(16)-Mn(1)-O(3) 178.4(5) C(17)-Mn(1)-O(3) 93.3(4) C(15)-Mn(1)-O(3) 90.9(4) C(16)-Mn(1)-P(2) 92.5(4) C(17)-Mn(1)-P(2) 172.9(4) C(15)-Mn(1)-P(2) 94.5(4) O(3)-Mn(1)-P(2) 86.3(2) C(16)-Mn(1)-P(1) 92.4(4) C(17)-Mn(1)-P(1) 89.8(4) C(15)-Mn(1)-P(1) 177.5(4) O(3)-Mn(1)-P(1) 88.5(2) P(2)-Mn(1)-P(1) 83.07(12) S(1)-O(3)-Mn(1) 124.4(5) C(3)-P(1)-C(6) 110.1(8) C(3)-P(1)-C(2) 105.2(8) C(6)-P(1)-C(2) 105.1(8) C(3)-P(1)-Mn(1) 118.4(5) C(6)-P(1)-Mn(1) 112.4(6) C(2)-P(1)-Mn(1) 104.4(5)

C(1)-P(2)-C(12) 103.4(6) C(1)-P(2)-C(9) 100.5(6) C(12)-P(2)-C(9) 105.6(6) C(1)-P(2)-Mn(1) 109.1(4) C(12)-P(2)-Mn(1) 120.0(4) C(9)-P(2)-Mn(1) 115.9(4) O(4)-S(1)-O(5) 117.7(7) O(4)-S(1)-O(3) 113.4(6) O(5)-S(1)-O(3) 114.4(5) O(4)-S(1)-C(18) 105.3(7) O(5)-S(1)-C(18) 103.0(6) O(3)-S(1)-C(18) 100.2(6) C(3)-C(5)-H(5A) 109.5 C(3)-C(5)-H(5B) 109.5 H(5A)-C(5)-H(5B) 109.5 C(3)-C(5)-H(5C) 109.5 H(5A)-C(5)-H(5C) 109.5 H(5B)-C(5)-H(5C) 109.5 C(6)-C(7)-H(7A) 109.5 C(6)-C(7)-H(7B) 109.5 H(7A)-C(7)-H(7B) 109.5 C(6)-C(7)-H(7C) 109.5 H(7A)-C(7)-H(7C) 109.5 H(7B)-C(7)-H(7C) 109.5 C(6)-C(8)-H(8A) 109.5 C(6)-C(8)-H(8B) 109.5 H(8A)-C(8)-H(8B) 109.5 C(6)-C(8)-H(8C) 109.5 H(8A)-C(8)-H(8C) 109.5 H(8B)-C(8)-H(8C) 109.5 C(3)-C(5P)-H(5PA) 109.5 C(3)-C(5P)-H(5PB) 109.5

S27

H(5PA)-C(5P)-H(5PB) 109.5 C(3)-C(5P)-H(5PC) 109.5 H(5PA)-C(5P)-H(5PC) 109.5 H(5PB)-C(5P)-H(5PC) 109.5 C(6)-C(7P)-H(7PA) 109.5 C(6)-C(7P)-H(7PB) 109.5 H(7PA)-C(7P)-H(7PB) 109.5 C(6)-C(7P)-H(7PC) 109.5 H(7PA)-C(7P)-H(7PC) 109.5

H(7PB)-C(7P)-H(7PC) 109.5 C(6)-C(8P)-H(8PA) 123.3 C(6)-C(8P)-H(8PB) 108.0 H(8PA)-C(8P)-H(8PB) 105.6 C(6)-C(8P)-H(8PC) 109.3 H(8PA)-C(8P)-H(8PC) 100.5 H(8PB)-C(8P)-H(8PC) 109.5

S28

Table S4. Torsion angles [°] for 2.

P(2)-C(1)-C(2)-P(1) 47.4(12) C(4)-C(3)-P(1)-C(6) -173.2(14) C(5)-C(3)-P(1)-C(6) 51.4(16) C(5P)-C(3)-P(1)-C(6) 91(3) C(4)-C(3)-P(1)-C(2) 74.1(14) C(5)-C(3)-P(1)-C(2) -61.3(16) C(5P)-C(3)-P(1)-C(2) -21(3) C(4)-C(3)-P(1)-Mn(1) -42.0(16) C(5)-C(3)-P(1)-Mn(1) -177.4(12) C(5P)-C(3)-P(1)-Mn(1) -137(3) C(8P)-C(6)-P(1)-C(3) -144(3) C(7P)-C(6)-P(1)-C(3) 48(4) C(8)-C(6)-P(1)-C(3) -84.0(19) C(7)-C(6)-P(1)-C(3) 50(2) C(8P)-C(6)-P(1)-C(2) -31(3) C(7P)-C(6)-P(1)-C(2) 161(4) C(8)-C(6)-P(1)-C(2) 29(2) C(7)-C(6)-P(1)-C(2) 163(2) C(8P)-C(6)-P(1)-Mn(1) 81(3) C(7P)-C(6)-P(1)-Mn(1) -87(4) C(8)-C(6)-P(1)-Mn(1) 141.8(17) C(7)-C(6)-P(1)-Mn(1) -84(2) C(1)-C(2)-P(1)-C(3) -173.9(10) C(1)-C(2)-P(1)-C(6) 69.9(12) C(1)-C(2)-P(1)-Mn(1) -48.5(10) C(2)-C(1)-P(2)-C(12) 104.3(11)

C(2)-C(1)-P(2)-C(9) -146.7(10) C(2)-C(1)-P(2)-Mn(1) -24.5(11) C(14)-C(12)-P(2)-C(1) -45.9(10) C(13)-C(12)-P(2)-C(1) -170.9(10) C(14)-C(12)-P(2)-C(9) -151.0(9) C(13)-C(12)-P(2)-C(9) 84.0(10) C(14)-C(12)-P(2)-Mn(1) 75.8(10) C(13)-C(12)-P(2)-Mn(1) -49.3(10) C(11)-C(9)-P(2)-C(1) -53.1(10) C(10)-C(9)-P(2)-C(1) 179.0(9) C(11)-C(9)-P(2)-C(12) 54.2(11) C(10)-C(9)-P(2)-C(12) -73.7(10) C(11)-C(9)-P(2)-Mn(1) -170.4(8) C(10)-C(9)-P(2)-Mn(1) 61.7(9) Mn(1)-O(3)-S(1)-O(4) -67.0(8) Mn(1)-O(3)-S(1)-O(5) 71.9(8) Mn(1)-O(3)-S(1)-C(18) -178.7(6) F(3)-C(18)-S(1)-O(4) 177.3(10) F(2)-C(18)-S(1)-O(4) 57.0(12) F(1)-C(18)-S(1)-O(4) -63.0(12) F(3)-C(18)-S(1)-O(5) 53.4(12) F(2)-C(18)-S(1)-O(5) -66.9(12) F(1)-C(18)-S(1)-O(5) 173.1(11) F(3)-C(18)-S(1)-O(3) -64.8(11) F(2)-C(18)-S(1)-O(3) 174.9(10) F(1)-C(18)-S(1)-O(3) 54.9(12)

________________________________________________________________

S29

Figure S27. ORTEP plot (50% probability, 130 K) for complex 2

Procedure S9. General procedure for the catalytic hydration of nitriles with complex 2

In the glovebox, a THF solution of the corresponding nitrile (0.46 mmol) was added dropwise to a yellow THF solution of 2 (5 mg, 0.0092 mmol, or 10 mg, 0.0184 mmol). The formed solution was transferred to a 25 mL Schlenk tube (Synthware Glass) (1 mL THF total volume), to which water (2 mL, 111 mmol) was added to form an emulsion, which evolved to a solution upon heating. The reaction mixture was stirred into an oil bath at 100 ºC during 18 h. After that, the solvent and volatiles were removed under reduced pressure in the inert gas/ vacuum double manifold and the residue was chromatographed on a silica gel column with hexanes/ethyl acetate mixtures as the eluent. The solvents of the collected fractions were evaporated under vacuum, the remaining solids were recrystallized from acetone and finally washed with fresh hexanes. Characterization of amides 2a-j. 2a (50 mg, 90%); m.p. 126-128 ºC (lit.1 m.p. 126-127 ºC). 1H (400 MHz, DMSO-d6) 7.97 (bs, 1H), 7.87 (dt, 3JHH = 7 Hz, 4JHH = 2 Hz, 2H), 7.51 (tt, 3JHH = 7.3 Hz, 4JHH = 2 Hz, 1H), 7.44 (tdd, 3JHH = 7.6 Hz, 4JHH = 2 Hz, 5JHH = 1 Hz, 2H), 7.35 (bs, 1H). 13C{1H} (100 MHz) 167.9, 134.3, 131.2, 128.2, 127.4. MS (EI) m/z 121 [M+ (100)], 122 [M+1 (9 ± 0.5)], 123 [M+2 (

S30

Figure S28. 1H NMR (400 MHz, DMSO-d6) aromatic region of the spectrum of isolated benzamide from optimized model reaction

7.057.107.157.207.257.307.357.407.457.507.557.607.657.707.757.807.857.907.958.008.058.108.158.20f1 (ppm)

1.0

0

2.2

6

1.1

3

2.2

6

0.9

7

7.3

5

7.4

37.4

47.4

6

7.5

07.5

17.5

3

7.8

67.8

77.8

87.8

9

7.9

7

S31

Figure S29. 1H NMR (400 MHz, DMSO-d6) spectrum of isolated benzamide from optimized model

reaction

Figure S30. 13C{1H} NMR (100 MHz, DMSO-d6) spectrum of isolated benzamide from optimized

model reaction

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.0

02

.26

1.1

32

.26

0.9

7

2.4

92.5

02.5

02.5

02.5

1

3.3

5

7.3

57.4

37.4

47.4

67.5

07.5

17.5

37.8

67.8

77.8

87.8

97.9

7

122124126128130132134136138140142144146148150152154156158160162164166168170172174f1 (ppm)

127.4

3128.1

8

131.1

9

134.2

5

167.8

9

S32

Figure S31. MS(EI) of isolated benzamide from optimized model reaction

2b (77 mg, 88%); m.p. 184-185 ºC (lit.2 m.p. 182-183 ºC). 1H (400 MHz, CDCl3/DMSO-d6) 8.04 (bs, 1H), 8.01 (d, J = 8.2 Hz, 2H), 7.63 (d, J = 8.1 Hz, 2H), 7.25 (bs, 1H). 13C{1H} (100 MHz) 167.3, 137.5, 131.8 (q, 1JCF = 32.2 Hz), 128.1, 124.8 (q, 3JCF = 3.7 Hz), 122.2. 19F (376 MHz) -60.3 (s). MS (EI) m/z 189 (M+).

Figure S32. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-

trifluoromethylbenzamide

7.157.207.257.307.357.407.457.507.557.607.657.707.757.807.857.907.958.008.058.10f1 (ppm)

1.0

0

2.1

1

3.0

9

M1

7.2

5

7.6

3

7.6

5

8.0

08.0

38.0

4

S33

Figure S33. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-


Figure S34. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated p-


115.5116.0116.5117.0117.5118.0118.5119.0119.5120.0120.5121.0121.5122.0122.5123.0123.5124.0124.5125.0125.5126.0126.5127.0127.5128.0128.5129.0129.5f1 (ppm)

119.5

298

122.2

365

124.7

410

124.7

774

124.8

143

124.8

496

124.9

442

127.6

521

128.0

648

-61.9-61.8-61.7-61.6-61.5-61.4-61.3-61.2-61.1-61.0-60.9-60.8-60.7-60.6-60.5-60.4-60.3-60.2-60.1-60.0-59.9-59.8-59.7-59.6-59.5-59.4-59.3-59.2-59.1-59.0f1 (ppm)

-60.7

5

-60.3

2-60.3

1-60.2

5-60.2

1-60.2

0

-60.0

2

S34

Figure S35. MS(EI) of p-trifluoromethylbenzamide

2c (57 mg, 89%); m.p. 154-156 ºC (lit.3 m.p. 153-154 ºC). 1H (400 MHz, CDCl3/DMSO-d6) 7.92 (dd, 3JHH = 8.6 Hz, 4JHF = 5.6 Hz, 2H), 7.89 (bs, 1H), 7.22 (bs, 1H), 7.14 (t, 3JHH = 3J HF = 8.7 Hz, 2H). 13C{1H} (100 MHz) 165.1, 162.6, 130.4, 129.9 (d, 3JCF = 8.9 Hz), 114.7 (d, 1JCF = 21.5 Hz). 19F (376 MHz) -107.5 (tt, 3JFH = 8.6 Hz, 4JFH = 5.5 Hz). MS (EI) m/z 139 (M+).

Figure S36. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-fluorobenzamide

6.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.4f1 (ppm)

1.0

0

1.0

4

M1 M2

7.1

157

7.1

351

7.1

374

7.1

391

7.1

592

7.2

219

7.8

905

7.9

035

7.9

174

7.9

250

7.9

389

8.1

264

S35

Figure S37. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-fluorobenzamide

Figure S38. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated p-fluorobenzamide

112114116118120122124126128130132134136138140142144146148150152154156158160162164166168f1 (ppm)

M1M2

114.5

7918

114.7

9396

129.8

5381

129.9

4188

130.4

2855

130.4

3851

162.5

7997

165.0

5781

166.8

8371

-107.72-107.70-107.68-107.66-107.64-107.62-107.60-107.58-107.56-107.54-107.52-107.50-107.48-107.46-107.44-107.42-107.40-107.38-107.36-107.34-107.32-107.30f1 (ppm)

M1

-107.5

636

-107.5

491

-107.5

405

-107.5

341

-107.5

261

-107.5

176

-107.5

117

-107.5

033

-107.4

888

S36

Figure S39. MS(EI) of p-fluorobenzamide

2d (91 mg, 94%); m.p. 152-153 ºC (lit.4 m.p. 150 ºC). 1H (400 MHz, CDCl3/DMSO-d6) 8.05 (bs, 1H), 7.84 (bs, 1H). 13C{1H} (100 MHz) 158.5, 144.4-144.0 (m), 142.3-141.6 (m), 139.7-139.4 (m), 138.2-137.7 (m), 135.7-135.2 (m), 113.0-112.4 (m). 19F (376 MHz) -139.3 (dtd, 3JFF = 22 Hz, 4JFF = 6.2 Hz, 5JFF = 2.5 Hz), -151.7 (t, 3JFF = 21.2 Hz), -159.5 (tdd, 3JFF = 21.4 Hz, 4JFF = 6.6, 5JFF = 2.7 Hz). MS (EI) m/z 211 (M+).

Figure S40. 19F NMR (376 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-

pentafluorobenzamide

-159.9-159.8-159.7-159.6-159.5-159.4-159.3-159.2-152.0-151.9-151.8-151.7-151.6-151.5-151.4-151.3-139.6-139.5-139.4-139.3-139.2-139.1-139.0f1 (ppm)

M1 M2M3

-159.6

090

-159.5

939

-159.5

532

-159.5

371

-159.4

971

-159.4

794

-159.4

723

-151.7

321

-151.6

757

-151.6

196

-139.3

290

-139.3

241

-139.3

088

-139.3

055

-139.2

654

-139.2

487

-139.2

386

S37

Figure S41. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-


Figure S42. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated 2,3,4,5,6-


7.507.557.607.657.707.757.807.857.907.958.008.058.108.158.208.258.308.358.408.45f1 (ppm)

1.0

0

1.0

2

7.8

4

8.0

5

2030405060708090100110120130140150160170f1 (ppm)

38.8

939.1

039.3

139.5

239.7

339.9

440.1

5

52.1

4

77.7

878.1

178.4

4

112.3

6112.3

9112.4

1112.6

2112.8

2112.8

3112.8

6112.9

5

135.1

6135.4

3135.6

6137.7

3137.9

4138.1

5139.3

5139.5

4139.7

3141.5

9141.7

4142.2

7144.0

7144.2

3144.4

3

158.5

4

S38

Figure S43. MS(EI) of 2,3,4,5,6-pentafluorobenzamide

2e (50 mg, 90%); m.p. 154-156 ºC (lit.5 m.p. 158 ºC). MS (EI) m/z 122 (M+).

Figure S44. MS(EI) of isonicotinamide

S39

2f (51 mg, 91%); m.p. 130-132 ºC (lit.6 m.p. 129-131 ºC). MS (EI) m/z 122 (M+).

Figure S45. MS(EI) of nicotinamide

2g (39 mg, 70%); m.p. 106-108 ºC (lit.7 m.p. 105-106 ºC). 1H (400 MHz, DMSO-d6) 8.62 (d, J = 4.4 Hz, 1H), 8.11 (bs, 1H), 8.04 (d, J = 7.7 Hz, 1H), 7.97 (td, J = 7.6 Hz, 1.6 Hz, 1H), 7.64 (bs, 1H), 7.58 (ddd, J = 7.4 Hz, 4.7 Hz, 1.3 Hz, 1H) 13C{1H} (100 MHz) 166.0, 150.3, 148.4, 137.6, 126.4, 121.9. MS (EI) m/z 122 (M+).

Figure S46. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated picolinamide

7.47.57.67.77.87.98.08.18.28.38.48.58.68.7f1 (ppm)

1.0

0

0.8

2

1.0

6

1.0

4

0.8

5

1.0

7

3.0

0

1.9

57.5

627

7.5

658

7.5

745

7.5

778

7.5

812

7.5

844

7.5

931

7.5

962

7.6

462

7.9

529

7.9

568

7.9

723

7.9

760

7.9

911

7.9

950

8.0

322

8.0

515

8.1

140

8.6

184

8.6

295

S40

Figure S47. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated picolinamide

Figure S48. MS(EI) of picolinamide

116118120122124126128130132134136138140142144146148150152154156158160162164166168170f1 (ppm)

121.8

8

126.4

2

137.6

1

148.4

3

150.2

8

166.0

2

S41

2h (65 mg, 93%); m.p. 166-168 ºC (lit.8 m.p. 166 ºC). 1H (400 MHz, CDCl3/DMSO-d6) 7.83 (ddd, 3JHH = 8.8 Hz, 4JHH = 3.6 Hz, 5JHH = 1.6 Hz, 2H), 7.70 (bs, 1H), 6.93 (bs, 1H), 6.87 (ddd, 3JHH = 8.8 Hz, 4JHH = 3.6 Hz, 5JHH = 1.6 Hz, 2H), 3.78 (s, 3H). 13C{1H} (100 MHz) 167.8, 161.5, 129.2, 126.2, 112.9, 54.9. MS (EI) m/z 151 (M+).

Figure S49. 1H NMR (400 MHz, CDCl3/DMSO-d6) spectrum of isolated p-methoxybenzamide

Figure S50. 13C{1H} NMR (100 MHz, CDCl3/DMSO-d6) spectrum of isolated p-methoxybenzamide

3.63.73.83.94.04.16.66.76.86.97.07.17.27.37.47.57.67.77.87.9f1 (ppm)

1.0

0

2.1

4

3.1

7

3.1

5

0.9

3

2.1

7

3.7

8

6.8

56

.86

6.8

66

.88

6.8

86

.89

6.9

3

7.7

0

7.8

17

.81

7.8

27

.83

7.8

47

.84

100105110115120125130135140145150155160165170175180185f1 (ppm)

112.9

5

126.2

0

129.1

7

161.4

5

167.7

8

S42

Figure S51. MS(EI) of p-methoxybenzamide

2i (56 mg, 90%); m.p. 160-162 ºC (lit.9 m.p. 162-163 ºC). MS (EI) m/z 135 (M+).

Figure S52. MS(EI) of p-toluamide

S43

2j (47 mg, 93%); m.p. 136-138 ºC (lit.10 m.p. 141-142 ºC). 1H (400 MHz, DMSO-d6) 7.78 (s, 1H), 7.75 (bs, 1H), 7.36 (bs, 1H), 7.09 (s, 1H), 6.58 (s, 1H). 13C{1H} (100 MHz) 159.4, 147.9, 144.9, 113.5, 111.7. MS (EI) m/z 111 (M+).

Figure S53. 1H NMR (400 MHz, DMSO-d6) spectrum of isolated furan-2-carbamide

Figure S54. 13C{1H} NMR (100 MHz, DMSO-d6) spectrum of isolated furan-2-carbamide

5.85.96.06.16.26.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)

1.0

0

1.1

6

1.1

1

2.2

0

M1

6.5

8

7.0

9

7.3

6

7.7

57.7

8

namely 2 mol% 2 2 and a mixture H2O/ THF in a 2:1 v/v ratio at 100 ºC,

104106108110112114116118120122124126128130132134136138140142144146148150152154156158160162164166168f1 (ppm)

111.6

5

113.5

0

144.8

7

147.9

5

159.4

0

S44

Figure S55. MS(EI) of furan-2-carbamide

References 1 Liu, K. T.; Shih, M. H.; Huang, H. W.; Hu, C. J. Synthesis 1988, 715. 2 Owston, N. A.; Parker, A. J.; Williams, J. M. J. Org. Lett. 2007, 9, 73-75. 3 Sharma, S. K.; Bishopp, S. D.; Allen, C. L.; Lawrence, R.; Bamford, M. J.; Lapkin, A. A.; Plucinski, P.; Watson, R. J.; Williams, J. M. J. Tetrahedron Lett. 2011, 52, 4252-4255. 4 Barbour, A. K.; Buxton, M. W.; Coe, P. L.; Stephens, R.; Tatlow, J. C. J. Chem. Soc. 1961, 808-817. 5 Balicki, R.; Kaczmarek, L. Synth. Commun. 1993, 23, 3149. 6 Crisóstomo, C.; Crestani, M. G.; García, J. J. Inorg. Chim. Acta 2010, 363, 1092-1096 . 7 Katritzky, A. R.; Pilarski, B.; Urodgi, L. Synthesis 1989, 949. 8 Ali, M. A.; Punniyamurthy, T. Adv. Synth. Catal. 2010, 352, 288. 9 Zhang, L.; Wang, S.; Zhou, S.; Yang, G.; Sheng, E. J. Org. Chem. 2016, 71, 3149-3153. 10 Jie, J.; Fang, J. J. Org. Chem. 2003, 68, 1158.

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