Electronic Supplementary Information (ESI) for and ... · Goodness of fit on F2 1.093 1.057 R1 [I > 2 (I)] R1 = 0.0489 0.0267 wR2 [I > 2 (I)] 0.1363 0.0705 R indices (all data) R1

S-1

Electronic Supplementary Information (ESI) for

Catalytic transformation of bio-derived furans to valuable ketoacids

and diketones by water-soluble ruthenium catalysts

Kavita Gupta,a Deepika Tyagi,a Ambikesh D. Dwivedi,a Shaikh M. Mobina and Sanjay K.

Singh*a,b

aDiscipline of Chemistry, School of Basic Sciences, Indian Institute of Technology (IIT)

Indore, Indore 452 017, Madhya Pradesh, India. E-mail: [email protected]

bCentre for Material Science and Engineering, Indian Institute of Technology (IIT)

Indore, Indore 452 017, Madhya Pradesh, India

Schematic presentation for the synthesis of arene-ruthenium(II) complexes

RuCl

Cl

RuCl

Cl

R

R

[Ru]-2

[Ru]-1

NNH2

Ru

Cl

R

N

NH2(2 equiv.)

MeOHstir, 4 h, r.t.

Cl

R=

Ru

Ph3P

R

N

NH2

2Cl

[Ru]-3

PPh3

MeOHstir, 4 h, r.t.

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2015

S-2

Single-crystal X-ray diffraction studies

Single crystal X-ray structural studies of [Ru]-1 and [Ru]-2 were executed on a CCD Agilent

Technologies (Oxford Diffraction) SUPER NOVA diffractometer. Using graphite-

monochromated Mo Kα radiation (λα = 0.71073 Å) based diffraction, data were collected at

150(2) K by the standard ‘phi-omega’ scan techniques, then scaled and reduced using

CrysAlisPro RED software. The extracted data were evaluated using the CrysAlisPro CCD

software. The structures were solved by direct methods using SHELXS-97, and refined by full

matrix least-squares with SHELXL-97, refining on F2.1 The positions of all the atoms were

determined by direct methods. All non-hydrogen atoms were refined anisotropically. The

remaining hydrogen atoms were placed in geometrically constrained positions and refined with

isotropic temperature factors, generally 1.2Ueq of their parent atoms. Crystal structures were

drawn with the help of ORTEP-3 (Fig. 1). The crystal and refinement data are summarized in

Table S1. Bond lengths and bond angles are summarized in Table S1 and S2 (†ESI). The CCDC

numbers 1401711 and 1402536 contain the supplementary crystallographic data for [Ru]-1 and

[Ru]-2 respectively.

References

(1) G. M. Sheldrick, Acta Crystallogr. Sect. A, 2008, 64, 112-122 (Program for Crystal

Structure Solution and Refinement, University of Goettingen, Göttingen, Germany, 1997).

S-3

Table S1 Single crystal X-ray refinement data for complexes [Ru]-1 and [Ru]-2

[Ru]-1 [Ru]-2

Empirical formula C15H14ClN2Ru C19H22Cl2N2Ru

Formula weight (g mol-1) 358 450.36

Temperature (K) 150(2) 150(2)

Wavelength (Å) 1.5418 1.5418

Crystal system

Space group

Triclinic

P -1

Monoclinic

P 21/c

Crystal size (mm) 0.33 x 0.26 x 0.21 0.33 x 0.26 x 0.21

a (Å) 7.6680(5) 17.0720(2)

b (Å) 8.3022(6) 12.30860(10)

c (Å) 13.5405(6) 9.10130(10)

α (º) 83.606(5) 90

β (º) 81.922(5) 100.9000(10)

γ (º) 70.403(6) 90

V (Å3) 802.11(9) 1877.97(3)

Z 2 4

calcd (g cm-3) 1.76 1.593

μ (mm-1) 11.044 9.382

F(000) 424 912

range, (º) 3.30 to 72.68 4.46 to 71.35

Index ranges -9<=h<=6; -19<=h<=20;

S-4

-9<=k<=10;

-16<=l<=16

-14<=k<=13;

-11<=l<=9

Completeness to max 94.6% 98.4 %

No. of data collected/unique data 4800 / 3022 [R(int) =

0.0300]

11844 / 3586 [R(int) =

0.0199]

Absorption correction Semi-empirical from

equivalents

Semi-empirical from

equivalents

No. of parameters/restraints 3022 / 0 / 208 0.2433 and 0.1478

Refinement method full-matrix least-squares

on F2

full-matrix least-squares

on F2

Goodness of fit on F2 1.093 1.057

R1 [I > 2(I)] R1 = 0.0489 0.0267

wR2 [I > 2(I)] 0.1363 0.0705

R indices (all data) R1 = 0.0493, wR2 =

0.1368

R1 = 0.0271, wR2 =

0.0709

Largest diff peak and hole, e Å-3 2.989 and -4.032 0.628 and -0.723

S-5

Table S2 Selected bond lengths (Å) for complex [Ru]-1 and [Ru]-2

[Ru]-1 [Ru]-2

Ru(1)-N(1)

Ru(1)-N(2)

Ru(1)-C(12)

Ru(1)-C(14)

Ru(1)-C(11)

Ru(1)-C(10)

Ru(1)-C(13)

Ru(1)-C(15)

N(2)-H(2A)

N(2)-H(2B)

C(1)-C(2)

C(2)-C(3)

C(3)-C(4)

C(4)-C(5)

C(4)-C(9)

C(5)-C(6)

C(6)-C(7)

C(7)-C(8)

C(8)-C(9)

C(10)-C(11)

2.097(4)

2.126(4)

2.164(5)

2.175(5)

2.184(5)

2.186(5)

2.195(5)

2.201(5)

2.4085(11)

1.322(7)

1.376(6)

1.443(6)

0.9200

0.9200

1.415(7)

1.358(8)

1.404(8)

1.417(8)

1.418(7)

1.374(9)

Ru(1)-N(1)

Ru(1)-N(2)

Ru(1)-C(15)

Ru(1)-C(13)

Ru(1)-C(16)

Ru(1)-C(12)

Ru(1)-C(14)

Ru(1)-C(11)

Ru(1)-Cl(1)

N(1)-C(1)

N(1)-C(9)

N(2)-C(8)

N(2)-H(1N)

N(2)-H(2N)

C(1)-C(2)

C(2)-C(3)

C(3)-C(4)

C(4)-C(9)

C(4)-C(5)

C(5)-C(6)

2.0940(18)

2.1336(18)

2.164(2)

2.167(2)

2.189(2)

2.193(2)

2.198(2)

2.223(2)

2.3984(6)

1.325(3)

1.375(3)

1.452(3)

0.91(4)

0.93(4)

1.408(3)

1.359(4)

1.412(4)

1.411(3)

1.414(4)

1.362(5)

S-6

C(10)-C(15)

C(11)-C(12)

C(12)-C(13)

C(13)-C(14)

C(14)-C(15)

1.399(8)

1.374(7)

1.411(7)

1.393(9)

1.406(9)

1.409(8)

1.407(8)

1.415(8)

1.403(8)

C(6)-C(7)

C(7)-C(8)

C(8)-C(9)

C(10)-C(11)

C(11)-C(16)

C(11)-C(12)

C(12)-C(13)

C(13)-C(14)

C(14)-C(15)

C(14)-C(17)

C(15)-C(16)

C(17)-C(19)

C(17)-C(18)

1.412(4)

1.360(3)

1.404(3)

1.498(4)

1.408(4)

1.419(4)

1.405(4)

1.426(4)

1.402(4)

1.512(3)

1.421(3)

1.509(5)

1.511(4)

S-7

Table S3 Selected bond angles (°) for complex [Ru]-1 and [Ru]-2

[Ru]-1 [Ru]-2

N(1)-Ru(1)-N(2)

N(1)-Ru(1)-C(12)

N(2)-Ru(1)-C(12)

N(1)-Ru(1)-C(14)

N(2)-Ru(1)-C(14)

C(12)-Ru(1)-C(14)

N(1)-Ru(1)-C(11)

N(2)-Ru(1)-C(11)

C(12)-Ru(1)-C(11)

C(14)-Ru(1)-C(11)

N(1)-Ru(1)-C(10)

N(2)-Ru(1)-C(10)

C(12)-Ru(1)-C(10)

C(14)-Ru(1)-C(10)

C(11)-Ru(1)-C(10)

N(1)-Ru(1)-C(13)

N(2)-Ru(1)-C(13)

C(12)-Ru(1)-C(13)

C(14)-Ru(1)-C(13)

C(11)-Ru(1)-C(13)

C(10)-Ru(1)-C(13)

78.66(16)

132.07(18)

90.49(18)

93.31(18)

142.72(19)

68.0(2)

169.56(19)

101.73(19)

37.8(2)

80.0(2)

146.3(2)

133.4(2)

67.6(2)

67.3(2)

37.2(2)

101.89(18)

107.85(19)

37.6(2)

37.8(2)

67.9(2)

79.9(2)

N(1)-Ru(1)-N(2)

N(1)-Ru(1)-C(15)

N(2)-Ru(1)-C(15)

N(1)-Ru(1)-C(13)

N(2)-Ru(1)-C(13)

C(15)-Ru(1)-C(13)

N(1)-Ru(1)-C(16)

N(2)-Ru(1)-C(16)

C(15)-Ru(1)-C(16)

C(13)-Ru(1)-C(16)

N(1)-Ru(1)-C(12)

N(2)-Ru(1)-C(12)

C(15)-Ru(1)-C(12)

C(13)-Ru(1)-C(12)

C(16)-Ru(1)-C(12)

N(1)-Ru(1)-C(14)

N(2)-Ru(1)-C(14)

C(15)-Ru(1)-C(14)

C(13)-Ru(1)-C(14)

C(16)-Ru(1)-C(14)

C(12)-Ru(1)-C(14)

78.71(7)

146.96(8)

91.87(8)

131.34(9)

148.45(9)

67.69(9)

111.66(8)

98.99(9)

38.09(9)

79.91(9)

101.29(8)

165.47(9)

80.23(9)

37.58(10)

67.31(9)

169.35(8)

111.92(8)

37.49(9)

38.12(9)

68.36(9)

68.61(9)

S-8

N(1)-Ru(1)-C(15)

N(2)-Ru(1)-C(15)

C(12)-Ru(1)-C(15)

C(14)-Ru(1)-C(15)

C(11)-Ru(1)-C(15)

C(10)-Ru(1)-C(15)

C(13)-Ru(1)-C(15)

N(1)-Ru(1)-Cl(1)

N(2)-Ru(1)-Cl(1)

C(12)-Ru(1)-Cl(1)

C(14)-Ru(1)-Cl(1)

C(11)-Ru(1)-Cl(1)

C(10)-Ru(1)-Cl(1)

C(13)-Ru(1)-Cl(1)

C(15)-Ru(1)-Cl(1)

C(1)-N(1)-C(9)

C(1)-N(1)-Ru(1)

C(9)-N(1)-Ru(1)

C(8)-N(2)-Ru(1)

C(8)-N(2)-H(2A)

Ru(1)-N(2)-H(2A)

C(8)-N(2)-H(2B)

Ru(1)-N(2)-H(2B)

111.7(2)

169.24(19)

80.3(2)

37.4(2)

67.6(2)

37.4(2)

67.9(2)

84.43(11)

84.98(12)

141.50(15)

130.87(15)

106.01(16)

88.22(14)

166.50(15)

98.73(15)

118.2(4)

126.4(3)

115.2(3)

112.2(3)

109.2

109.2

109.2

109.2

N(1)-Ru(1)-C(11)

N(2)-Ru(1)-C(11)

C(15)-Ru(1)-C(11)

C(13)-Ru(1)-C(11)

C(16)-Ru(1)-C(11)

C(12)-Ru(1)-C(11)

C(14)-Ru(1)-C(11)

N(1)-Ru(1)-Cl(1)

N(2)-Ru(1)-Cl(1)

C(15)-Ru(1)-Cl(1)

C(13)-Ru(1)-Cl(1)

C(16)-Ru(1)-Cl(1)

C(12)-Ru(1)-Cl(1)

C(14)-Ru(1)-Cl(1)

C(11)-Ru(1)-Cl(1)

C(1)-N(1)-C(9)

C(1)-N(1)-Ru(1)

C(9)-N(1)-Ru(1)

C(8)-N(2)-Ru(1)

C(8)-N(2)-H(1N)

Ru(1)-N(2)-H(1N)

C(8)-N(2)-H(2N)

Ru(1)-N(2)-H(2N)

92.81(8)

128.11(9)

68.15(9)

67.82(9)

37.23(9)

37.49(9)

81.13(9)

85.66(5)

84.18(6)

125.21(7)

88.49(7)

162.68(7)

110.35(7)

94.59(7)

146.78(7)

117.90(19)

126.28(16)

115.76(14)

111.72(13)

111(2)

109(2)

102(2)

112(2)

S-9

H(2A)-N(2)-H(2B)

N(1)-C(1)-C(2)

C(3)-C(2)-C(1)

C(2)-C(3)-C(4)

C(3)-C(4)-C(5)

C(3)-C(4)-C(9)

C(5)-C(4)-C(9)

C(6)-C(5)-C(4)

C(5)-C(6)-C(7)

C(8)-C(7)-C(6)

C(7)-C(8)-C(9)

C(7)-C(8)-N(2)

C(9)-C(8)-N(2)

N(1)-C(9)-C(8)

N(1)-C(9)-C(4)

C(8)-C(9)-C(4)

C(11)-C(10)-C(15)

C(11)-C(10)-Ru(1)

C(15)-C(10)-Ru(1)

C(10)-C(11)-C(12)

C(10)-C(11)-Ru(1)

C(12)-C(11)-Ru(1)

C(13)-C(12)-C(11)

107.9

122.4(5)

120.1(5)

119.4(5)

124.3(5)

117.7(5)

118.0(5)

120.5(5)

121.0(5)

120.3(5)

119.8(5)

124.2(5)

116.1(4)

117.3(4)

122.2(4)

120.5(4)

121.2(5)

71.3(3)

71.9(3)

119.5(5)

71.5(3)

70.3(3)

120.7(5)

H(1N)-N(2)-H(2N)

N(1)-C(1)-C(2)

C(3)-C(2)-C(1)

C(2)-C(3)-C(4)

C(9)-C(4)-C(3)

C(9)-C(4)-C(5)

C(3)-C(4)-C(5)

C(6)-C(5)-C(4)

C(5)-C(6)-C(7)

C(8)-C(7)-C(6)

C(7)-C(8)-C(9)

C(7)-C(8)-N(2)

C(9)-C(8)-N(2)

N(1)-C(9)-C(8)

N(1)-C(9)-C(4)

C(8)-C(9)-C(4)

C(16)-C(11)-C(12)

C(16)-C(11)-C(10)

C(12)-C(11)-C(10)

C(16)-C(11)-Ru(1)

C(12)-C(11)-Ru(1)

C(10)-C(11)-Ru(1)

C(13)-C(12)-C(11)

111(3)

122.9(2)

119.6(2)

119.6(2)

117.4(2)

118.4(2)

124.2(2)

119.8(2)

121.4(3)

119.7(3)

120.1(2)

123.4(2)

116.54(19)

117.07(19)

122.5(2)

120.4(2)

118.4(2)

120.9(2)

120.7(2)

70.09(13)

70.12(13)

130.76(18)

120.3(2)

S-10

C(13)-C(12)-Ru(1)

C(11)-C(12)-Ru(1)

C(12)-C(13)-C(14)

C(12)-C(13)-Ru(1)

C(14)-C(13)-Ru(1)

C(15)-C(14)-C(13)

C(15)-C(14)-Ru(1)

C(13)-C(14)-Ru(1)

C(14)-C(15)-C(10)

C(14)-C(15)-Ru(1)

C(10)-C(15)-Ru(1)

72.4(3)

71.9(3)

118.6(5)

70.0(3)

70.4(3)

121.2(5)

72.3(3)

71.9(3)

118.8(5)

70.3(3)

70.7(3)

C(13)-C(12)-Ru(1)

C(11)-C(12)-Ru(1)

C(12)-C(13)-C(14)

C(12)-C(13)-Ru(1)

C(14)-C(13)-Ru(1)

C(15)-C(14)-C(13)

C(15)-C(14)-C(17)

C(13)-C(14)-C(17)

C(15)-C(14)-Ru(1)

C(13)-C(14)-Ru(1)

C(17)-C(14)-Ru(1)

C(14)-C(15)-C(16)

C(14)-C(15)-Ru(1)

C(16)-C(15)-Ru(1)

C(11)-C(16)-C(15)

C(11)-C(16)-Ru(1)

C(15)-C(16)-Ru(1)

C(19)-C(17)-C(18)

C(19)-C(17)-C(14)

C(18)-C(17)-C(14)

70.22(13)

72.39(13)

121.9(2)

72.19(13)

72.09(13)

117.1(2)

123.8(2)

119.1(2)

69.97(13)

69.79(13)

129.82(17)

121.6(2)

72.54(13)

71.90(13)

120.7(2)

72.68(14)

70.01(13)

111.6(3)

114.1(3)

109.2(2)

S-11

Table S4 Catalytic transformation of furfural to LA in aqueous medium with different

arene-ruthenium(II) complexes based catalysts. Reaction Conditions: furfural (1.0

mmol), catalyst (1 mol%), formic acid (12 equiv.) and water (10 mL), T = 80 °C.

Entry Catalyst Conv./Sel.

1. [Ru]-2 >99/>99

2. [Ru]-3 17.6/>99

3. [Ru]-4 27/>99

4. [Ru]-5 50/>99

OO [Ru]-complex

HCOOH (12 equiv.)H2O, 80 °C

16 h

OHO

OFurfural LA

S-12

Table S5 Influence of additives on the catalytic transformation of furfural to LA in the

presence of [Ru]-2. Reaction Conditions: furfural (1.0 mmol), [Ru]-2 (1 mol%), and

water (10 mL).

Entry Additive T (°C) / t (h) Conv. (%)

1 formic acida 100/7 >99

2 formic acida 80/16 >99

3 formic acida 60/16 23

4 H2 gasb 80/16 n.r.

5 acetic acida 80/16 ~2

6 propionic acida 80/16 n.r.

7 iso-butyric acida 80/16 n.r.

a12 equivalents. bfrom balloon.

S-13

Figure S1 Influenece of temperature on the decomposition of formic acid (1 mmol) to

CO2 and H2 with [Ru]-2 catalyst (0.01 mmol).

Figure S2 Possible reaction mechanism for the transformation of furfural to LA.

RuN

NH2

Cl

RuN

NH2

OOCH

RuN

NH2

H RuN

NH

HH OO

RuN

NHCl

HCOOH

CO2

O O

HH

OOH

O CH2

OH2

O

OHO

OHO

HO

HO

HO

OH

HOOH

HO

O

OLevulinic acid

H2O

H2O

H2O

H2O

tautomerization

CH2

O

O

H2O

H

Furfural

S-14

The thermal stability studies were performed in NMR tubes by dissolving ca. 4 mg of each catalyst in 0.5

mL of D2O and heating the solution at 80 or 100 °C. The decomposition of the catalyst was monitored by 1H NMR spectra taken at certain intervals of time (0, 24, 48 and 72 h).

Figure S3 1H NMR spectra for the thermal stability of [Ru]-1 catalyst at 80 °C in D2O.

Figure S4 1H NMR spectra for the thermal stability of [Ru]-2 catalyst at 80 °C in D2O.

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

Deuterium Oxide

4.75

t = 0 h

t = 24 h

t = 48 h

t = 72 h

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0Chemical Shift (ppm)

Deuterium Oxide

4.75

t = 0 h

t = 24 h

t = 48 h

t = 72 h

S-15

Figure S5 1H NMR spectra for the thermal stability of [Ru]-2 catalyst at 80 °C and 100

°C in D2O.

Figure S6 Thermal gravimetric analysis (TGA) graph of a) [Ru]-1 and b) [Ru]-2.

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

Deuterium Oxide

4.75

t = 0 h

t = 24 h

t = 24 h100 °C

80 °C

S-16

Figure S7 Stability of [Ru]-2 catalyst towards recyclability for the catalytic

transformation of furfural to LA at 80 and 100 °C.

S-17

Spectral data of products obtained by catalytic transformation of bio-derived

furans

OH

O

O

Levulinic acid (LA): 1H NMR (400 MHz, CDCl3): δ (ppm) = 2.73 (t, 2H, J = 8 Hz), 2.59 (t, 2H,

J = 8 Hz), 2.17 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) = 206.65, 177.53, 37.69, 29.78,

27.64. HRMS (ESI) m/z: calculated 139.04 [C5H8O3 + Na+], found 139.036 [C5H8O3 + Na+].

O

OOH

3-Hydroxyhexane-2,5-dione (3-HHD): 1H NMR (400 MHz, CDCl3): δ (ppm) 4.33-4.30 (m,

1H), 3.75 (br, 1H) 2.95 (dd, 1H, J1 = 16 Hz, J2 = 4Hz), 2.82 (dd, 1H, J = 16 Hz, J2 = 4Hz), 2.22

(s, 3H), 2.18 (s, 3H), 13C NMR (100 MHz, CDCl3): δ (ppm) = 209.15, 207.09, 73.76, 46.11,

30.81, 25.38. HRMS (ESI) m/z: calculated 153.05 [C5H10O3 + Na+], found 153.05 [C5H10O3 +

Na+].

O

O

HO

1-Hydroxyhexane-2,5-dione (1-HHD): 1H NMR (400MHz, CDCl3): δ (ppm) = 4.31 (s, 2H),

2.82 (t, 2H, J = 8 Hz), 2.61 (t, 2H, J = 8 Hz), 2.17 (s, 3H).

O

O

Hexane-2,5-dione (HD): 1H NMR (400 MHz, CDCl3): δ (ppm) = 2.69 (s, 4H), 2.18 (s, 6H).

S-18

NMR Spectra of arene-ruthenium(II) complexes

Figure S8 1H NMR spectrum of complex [Ru]-1.

Ru

Cl N

NH2

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0Chemical Shift (ppm)

6.002.501.121.061.03

Deuterium Oxide

4.75

5.96

7.59

7.617.64

7.65

7.66

7.75

7.767.83

7.858.44

8.479.56

9.58

7.8 7.7 7.6Chemical Shift (ppm)

2.501.12 1.12

7.577.

597.

617.

637.64

7.65

7.667.

757.

767.83

7.85

S-19

Figure S9 13C NMR spectrum of complex [Ru]-1.

Ru

Cl N

NH2

155 150 145 140 135 130 125 120 115 110 105 100 95 90 85Chemical Shift (ppm)

84.7

4

123.

79127.

12

128.

2412

9.27

137.

8813

9.40

145.

30

156.

20

S-20

Figure S10 1H NMR spectrum of complex [Ru]-2.

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.033.021.121.071.051.00 0.97

0.900.91

1.041.06

2.10

2.142.602.

612.

632.

65

3.32

4.75

5.715.72

5.805.

815.91

5.926.03

6.04

7.63

7.65

7.727.

817.

827.88

7.90

8.50

8.529.

559.

56

9.5 9.0 8.5 8.0 7.5Chemical Shift (ppm)

1.051.021.00 0.97

7.63

7.65

7.727.

817.

827.88

7.908.50

8.529.

559.56

Ru

Cl N

NH26.0 5.9 5.8 5.7Chemical Shift (ppm)

1.071.02 0.97 0.97

6.04 6.03

5.92 5.

91

5.81

5.80 5.72

5.71

S-21

Figure S11 13C NMR spectrum of complex [Ru]-2.

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20Chemical Shift (ppm)

17.7

721

.07

30.4

0

48.8

5

82.0

882

.6883

.30

84.8

7

100.

8310

3.17

124.

1112

7.36

128.

4712

9.27

137.

8313

9.46

145.

27

156.

12

Ru

Cl N

NH2

S-22

140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160Chemical Shift (ppm)

41.2

7

Ru

Ph3P N

NH2

2

Figure S12 31P NMR spectrum of complex [Ru]-3.

S-23

Mass Spectra of arene ruthenium complexes

Figure S13 Mass spectrum of complex [Ru]-1


S-24


S-25

NMR Spectra of products obtained by catalytic transformation of bio-derived furans

OO OH

O

OHCOOH (12 equiv.), H2O,

80 oC, 16 h

1 mol% [Ru]-2

Levulinic acidFurfural

Figure S16 1H NMR spectrum of Levulinic acid.

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0Chemical Shift (ppm)

3.042.00

Chloroform-d

7.26

2.74

2.73

2.71

2.59

2.57

2.17

OOH

Oa b

c

bc2.7 2.6 2.5Chemical Shift (ppm)

2.002.00

2.74

2.73

2.71

2.61 2.

592.

57

bc

S-26

200 180 160 140 120 100 80 60 40 20Chemical Shift (ppm)

Chloroform-d

206.

66

177.

53

77.3

277

.00

76.6

9

37.6

9

29.7

827

.64

OH

O

O

Figure S17 13C NMR spectrum of Levulinic acid.

Figure S18 HRMS data of levulinic acid obtained from furfural.

S-27

Figure S19 1H NMR spectrum of the products obtained from the catalytic transformation

of furfural with 2 equivalents of formic acid.

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5Chemical Shift (ppm)

1.19 1.071.001.00 0.670.440.12 0.10

9.59

7.63

7.33

7.20

6.54

6.27

6.23

4.55

2.71

2.69

2.56

2.55

2.13

2.7 2.6Chemical Shift (ppm)

0.44 0.41

2.71 2.

692.

68

2.58 2.56

2.55

OO

OOH

O

O

OHa

b c

de

f g

h

i j

k

k j

d

a

c

b

e f gh

OO OH

O

OHCOOH (2 equiv.), H2O,

80 oC, 16 h

1 mol% [Ru]-2

Levulinic acidFurfural

OOH

Furfuryl alcohol

S-28

OO

O

O O

O

OHHCOOH (12 equiv.), H2O

80 oC, 16 h

1 mol% [Ru]-2

5-methylfurfural Hexane-2,5-dione 3-hydroxyhexane-2,5-dione


of 5-methylfurfuraldehyde.

4.0 3.5 3.0 2.5Chemical Shift (ppm)

3.061.301.151.00 0.94 0.500.33

4.35 4.34

4.33

4.32

3.00

2.99

2.95

2.94

2.87

2.86

2.83

2.81

2.69

2.41

2.25

2.21

2.18

O

O O

O

OH

a

b

a bc

de f

cd

ef

S-29

O

O

OH

a b c

d

e

ae

c

d

b

4.0 3.5 3.0 2.5Chemical Shift (ppm)

3.031.181.101.00 0.99

4.33 4.32

4.31

4.30

3.75 2.

972.

962.

932.

922.

842.

832.

802.

78

2.22

2.18

Figure S21 1H NMR spectrum of 3-hydroxyhexane-2,5-dione (after purification)

obtained from 5-methyl furfural.

S-30

Figure S22 13C NMR spectrum of 3-hydroxyhexane-2,5-dione (after purification)

obtained from 5-methyl furfural.

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30Chemical Shift (ppm)

Chloroform-d

25.3

8

30.8

1

46.1

1

73.7

6

207.

0920

9.15

O

O

OH

S-31

Figure S23 HRMS data of 3-hydroxyhexane-2,5-dione obtained from 5-methyl furfural.

OO

O

O O

O

OHHCOOH (12 equiv.), H2O

80 oC, 48 h

1 mol% [Ru]-2

3-hydroxyhexane-2,5-dione

HO

5-HMF

HO

1-hydroxyhexane-2,5-dione

OOH

O

Levulinic acid

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0Chemical Shift (ppm)

3.532.462.072.00

Chloroform-d

2.17

2.20

2.24

2.59

2.61

2.68

2.802.

822.

832.

932.

94

2.98

4.29

4.31

7.26

4.5 4.4 4.3 4.2 4.1Chemical Shift (ppm)

2.00

4.29

4.31

3.0 2.9 2.8 2.7 2.6 2.5Chemical Shift (ppm)

2.462.071.13 1.06

2.592.

612.

62

2.722.73

2.752.

802.82

2.83

2.922.93

2.94

2.97

2.98

O

O O

O

OH

HO

OOH

O

a b

c d e f gh

i j

k

ab c, j d, i

eh

fg k

S-32


of 5-hydroxymethyl-2-furfual (5-HMF).

Electronic Supplementary Information (ESI) for and ... · Goodness of fit on F2 1.093 1.057 R1 [I > 2 (I)] R1 = 0.0489 0.0267 wR2 [I > 2 (I)] 0.1363 0.0705 R indices (all data) R1

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