electronic supplementary information · 2019. 4. 1. · (p 2 o 5 h 2) 4], ptpop-iii: ptpop-i (225...

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Electronic Supplementary Information

Table of contents

Experimental section S2

a) General information S2

b) Method for the synthesis of binuclear platinum diphosphite complexes S4

c) General procedure for Ptpop photocatalysis for organic transformations S5

d) Procedure for the gram-scale photocatalysis S5

e) Procedure and details for measuring the kinetic isotope effect (KIE) for

photo-dehydrogenation of p-methoxybenzyl alcohol and 2-propanol

S6

Figure S1: Magnified ns TA spectrum of Ptpop-III (3 × 10-5

M) in the

presence of indoline (2 mM) in degassed MeOH recorded at 4 μs after laser

flash at room temperature

S7

Figure S2: 1H NMR spectrum of Ptpop-BF2-IV in the presence of

p-methoxybenzyl alcohol (30 equiv., 0.15 M) in CD3CN after light

irradiation for five minutes

S7

Characterization data of the products S8

NMR spectra of products S24

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2019

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Experimental section

a) General information

All chemicals, unless otherwise noted, were purchased from commercial sources

and were used without further purification. All solvents for photophysical studies

were of HPLC grade. Unless stated otherwise, all reactions were carried out under

nitrogen. Irradiation was performed using 365 nm and 410 nm LEDs illumination

instruments.

The nuclear magnetic resonance spectra were recorded on the Bruker AscendTM

400 MHz NMR spectrometer and the Bruker AscendTM

500 MHz NMR spectrometer

with tetramethylsilane (TMS) as an internal standard. High resolution mass spectra

were recorded using a Q Exactive mass spectrometer (Thermo Fisher Scientific, USA).

Elemental analyses were performed at the Institute of Chemistry of the Chinese

Academy of Sciences, Beijing. Gas chromatography-mass spectrometry (GC-MS)

analyses were performed with an Agilent Technologies 7890A Network GC System

equipped with an Agilent Technologies 5975C Network Mass Selective Detector

(MSD). Gas chromatography for measuring hydrogen gas evolution was performed

with an Agilent Technologies 7890A GC system with thermal conductivity detector

(TCD). High purity argon was used as both carrier and reference gas and an Agilent

HP-molesieve column (Model 19091P-MS4E, 5 Å molecular sieve, length = 30 m,

internal diameter = 0.320 mm, film thickness = 12 μm) was used for gas separation.

The absorption spectra were recorded on a Thermo Scientific Evolution 201

UV/Visible Spectrophotometer. The emission spectra were recorded on an Edinburg

spectrometer FLS-980 equipped with MCP-PMT detectors. Solutions for

photophysical studies were degassed by using a high vacuum line in a

two-compartment cell with five freeze-pump-thaw cycles. The emission quantum

yield was measured with quinine sulfate (Φ = 0.546) in 1.0 N H2SO4 as reference and

calculated by: Φs = Φr(Br/Bs)(ns/nr)2(Ds/Dr), in which the subscripts s and r refer to

sample and reference standard solution, respectively, n is the refractive index of the

solvents, D is the integrated emission intensity and Φ is the luminescence quantum

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yield. The excitation intensity B is calculated by: B = 1–10–AL

, where A is the

absorbance at the excitation wavelength and L is the optical path length (λ = 1 cm in

all cases). The refractive indices of the solvents at room temperature were taken from

standard sources. Emission lifetime measurements were performed on a Quanta Ray

GCR 150-10 pulsed Nd:YAG laser system with 355 nm output as excitation light

source. Emission quenching rate constants of substrates were obtained by the

Stern-Volmer equation : τo/τ = 1 + kq∙τo∙[Q], where τo is the emission lifetime of the

Pt(II) complex at a concentration of 6 × 10-6

M; τ is the emission lifetime of the Pt(II)

complex at the same concentration but with different concentrations of quencher; [Q]

is the concentration of quencher. The slope of the Stern-Volmer plot is kq∙τo and the

quenching rate constant, kq, can be estimated. Nanosecond time-resolved emission

measurements were performed on a LP920-KS Laser Flash Photolysis Spectrometer

(Edinburgh Instruments Ltd., Livingston, UK). The excitation source was the 355 nm

output (third harmonic) of a Nd:YAG laser (Spectra-Physics Quanta-Ray Lab-130

Pulsed Nd:YAG Laser). The signals were processed by a PC plug-in controller with

L900 software.

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b) Method for the synthesis of binuclear platinum diphosphite complexes

K4[Pt2(P2O5H2)4], Ptpop-I: Potassium tetrachloroplatinate(II) (400 mg), and

phosphorous acid (2.0 g) were dissolved in 8 mL of deionized water in 50 mL

round-bottom flask. The solution was stirred on the oil bath at 104 oC and heated for

12 h. After reaction, minimum of water was added to dissolve the light yellow green

residue, followed by precipitation of addition of methanol. The resulting suspension

was filtered and then the solid was washed successively with acetone and methanol. A

yellow green powder (Ptpop-I) could be obtained (70% yield). Ptpop-I: 31

P NMR

(162 MHz, D2O) δ = 65.95 (JP-Pt = 3073Hz).

[Bu4N]4[Pt2(P2O5H2)4], Ptpop-II: Ptpop-I (225 mg) and Bu4NCl (225 mg) were

dissolved in 10 mL of deionized water. The solution was placed on ice bath at 0 oC for

precipitation, green crystal (Ptpop-II) could be obtained (30% yield). Ptpop-II: 1

H

NMR (500 MHz, CD3OD) δ = 3.25 – 3.21 (m, 8H), 1.70 – 1.61 (m, 8H), 1.44 – 1.39

(m, 8H), 1.02 (t, J = 7.4 Hz, 12H). 31

P NMR (202 MHz, CD3OD) δ = 66.13 (JP-Pt =

3115 Hz).

[(C16H33)2(CH3)2N]4[Pt2(P2O5H2)4], Ptpop-III: Ptpop-I (225 mg) was dissolved in 10

mL deionized water, then addition of aqueous solution of [(C16H33)2(CH3)2N]Br (460

mg) resulted in precipitation, light green powder (Ptpop-III) could be obtained (90%

yield). Ptpop-III: 31

P NMR (162 MHz, CD3OD) δ = 65.79 (JP-Pt = 3062 Hz).

Elemental analysis calculated for C136H296N4O20P8Pt2: C, 55.45; H, 10.13; N, 1.90;

found: C, 55.67; H, 10.29; N, 1.96.

[(C16H33)2(CH3)2N]4[Pt2(P2O5(BF2)2)4], Ptpop-BF2-IV: In the glove box under a

dry argon atmosphere, 200 mg Ptpop-III were dissolved in 3 mL of neat F3B·OEt2

and stirred at room temperature for 4 days. The solvent was removed by vacuum

evaporation. The residue was dissolved in minimum dry, degassed THF. Vapor

diffusion of diethyl ether into the THF solution resulted in the precipitation of the

product (80% yield). Ptpop-BF2-IV: 19

F NMR (376 MHz, CD3CN) δ = -133.45 (d, J

= 63.5 Hz, 8F), -138.80 (d, J = 62.4 Hz, 8F). 31

P NMR (162 MHz, CD3CN) δ = 58.91

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(JP-Pt = 3133 Hz). Elemental analysis calculated for C136H288B8F16N4O20P8Pt2: C,

49.08; H, 8.72; N, 1.68; found: C, 49.27; H, 8.88; N, 1.83.

c) General procedure for Ptpop photocatalysis for organic transformations

The substrates and the binuclear platinum diphosphite complexes were dissolved

in solvents (3 mL) in a 15 mL reaction tube equipped with magnetic stirring bar. The

reaction tube was sealed and the reaction mixture was deaerated with nitrogen for 15

min. Then the reaction tube was irradiated by 410 nm or 365 nm LEDs. After reaction,

the organic layer was extracted with diethyl ether (3 × 5 mL). The combined organic

phases were washed with brine and dried over sodium sulphate. The solvent was

removed by rotary evaporation and purified by column chromatography on silica gel

using hexane/ethyl acetate (25:1) as the eluent.

d) Procedure for the gram-scale photocatalysis

1-Phenylethanol (10 mmol), 4-hydroxy-3-methoxybenzyl alcohol (8.1 mmol),

indoline (10 mmol) and isopropanol (20 mmol) were chosen as the substrates for

investigation. The binuclear platinum diphosphite complex and additives (nBu4NCl, if

needed) for the corresponding substrate were added to a 50 mL round-bottomed flask

equipped with magnetic stirring bar and containing the substrate and deuterated

solvents of the corresponding reaction condition. The reaction tube was sealed and the

reaction mixture was deaerated with nitrogen for 15 min. Then the reaction flask was

irradiated by 410 nm or 365 nm LEDs according to the reaction condition of the

substrate. The reaction progress was monitored with GC-FID. After complete

consumption of substrate, an aliquot of the reaction mixture was taken out and

examined by 1H NMR spectroscopy. The yield of photo-oxidation of 1-Phenylethanol,

4-hydroxy-3-methoxybenzyl alcohol, indoline was determined as isolated yields after

purification by flash chromatography. The yield of photo-oxidation of isopropanol

(which was conducted in CD3CN) was determined by 1H NMR spectroscopic

analysis.

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e) Procedure and details for measuring the kinetic isotope effect (KIE) for

photo-dehydrogenation of p-methoxybenzyl alcohol and 2-propanol

Reaction conditions were the same as the respective conditions for photocatalysis,

except that deuterated alcohol substrates were used. For the intermolecular

competition of photo-dehydrogenation of p-methoxybenzyl alcohol by Ptpop-I, a

mixture of 0.2 mmol of non-deuterated p-methoxybenzyl alcohol and 0.2 mmol of

p-(CH3O)C6H4CD2OH was used as the substrate. For the intramolecular competiton

of photo-dehydrogenation of p-methoxybenzyl alcohol by Ptpop-I, 0.4 mmol of

p-(CH3O)C6H4CH(D)OH was used as the substrate. Since the deuterated

p-methoxybenzaldehyde product (p-(CH3O)C6H4CDO) has 1H signals for the

aromatic protons but not the aldehyde (–CDO group), by comparing the integrals of

1H of aldehyde (~9.9 ppm) and that of the aromatic

1H (~7.0 and 7.7 ppm) of the

crude reaction mixture which contains both non-deuterated and deuterated aldehyde

products, the ratio of non-deuterated aldehyde to deuterated aldehyde product could

be determined. For the intermolecular competition reaction, the non-deuterated

aldehyde product was obtained as the major product, implying that the

photo-dehydrogenation of non-deuterated alcohol substrate proceeded faster. The ratio

of non-deuterated aldehyde to deuterated aldehyde is estimated as 0.77:0.23, giving a

KIE value of 3.35. For the intramolecular competition reaction (i.e.

p-(CH3O)C6H4CH(D)OH being the substrate), the major product was found to be the

deuterated aldehyde product, meaning that C–H bond cleavage proceeded faster than

C–D bond cleavage. The ratio of deuterated aldehyde to non-deuterated aldehyde is

estimated as 0.77:0.23, giving a KIE value of 3.35. The 1H NMR spectra for the above

results are shown in page S108. The KIE for photo-dehydrogenation of 2-propanol

was determined by using a 1:1 mixture of non-deuterated 2-propanol and

D8-2-propanol (CD3CD(OD)CD3) as substrate. The ratio of non-deuterated

(CH3COCH3) to deuterated (CD3COCD3) acetone was estimated as 4.2:1 with

GC-MS.

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Fig. S1 Magnified nanosecond time-resolved absorption spectrum of Ptpop-III (3 ×

10-5

M) in the presence of indoline (2 mM) in degassed MeOH recorded at 4 μs after

laser flash at room temperature. This absorption profile is long-lived with decay time

constant of 72 μs.

Fig. S2 1H NMR spectrum (500 MHz, from -5 to -11 ppm) of Ptpop-BF2-IV in the

presence of p-methoxybenzyl alcohol (30 equiv., 0.15 M) in CD3CN after light

irradiation for five minutes.

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Characterization data of the products

1H NMR (500 MHz, CDCl3) δ = 7.82 – 7.74 (m, 2H), 7.38 (dt, J = 14.9, 7.4 Hz, 2H), 2.61 (s, 3H),

2.43 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 198.49, 138.37, 137.15, 133.90, 128.81, 128.46, 125.61, 26.71,

21.36.

HRMS (ESI) (m/z): [M+H]+ calcd. for C9H11O: 135.0804, found: 135.0801.

1H NMR (500 MHz, CDCl3) δ = 7.94 (t, J = 1.7 Hz, 1H), 7.84 (d, J = 7.8 Hz, 1H), 7.57 – 7.53 (m,

1H), 7.42 (t, J = 7.9 Hz, 1H), 2.61 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 196.78, 138.59, 134.92, 133.06, 129.96, 128.42, 126.43, 26.68.

HRMS (ESI) (m/z): [M+H]+ calcd. for C8H8OCl: 155.0258, found: 155.0254.

1H NMR (500 MHz, CDCl3) δ = 7.97 (d, J = 8.1 Hz, 2H), 7.60 – 7.54 (m, 1H), 7.47 (t, J = 7.7 Hz,

2H), 2.62 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 198.20, 137.11, 133.13, 128.59, 128.32, 26.64.


1H NMR (500 MHz, CDCl3) δ = 8.22 (s, 1H), 8.16 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 7.7 Hz, 1H),

7.63 (t, J = 7.8 Hz, 1H), 2.67 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 196.65, 137.53, 131.46, 131.11, 129.54 (q, J = 3.6 Hz), 129.32,

125.13 (q, J = 3.8 Hz), 122.61, 26.62. 19

F NMR (376 MHz, CDCl3) δ = -62.83 (s, 3F).

HRMS (ESI) (m/z): [M+H]+ calcd. for C9H8OF3: 189.0522, found: 189.0516.

1H NMR (500 MHz, CDCl3) δ = 7.54 (d, J = 7.6 Hz, 1H), 7.50 – 7.47 (m, 1H), 7.37 (t, J = 7.9 Hz,

1H), 7.11 (dd, J = 8.2, 2.6 Hz, 1H), 3.85 (s, 3H), 2.60 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 197.99, 159.80, 138.46, 129.58, 121.13, 119.61, 112.33, 55.42,

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26.74.

HRMS (ESI) (m/z): [M+H]+ calcd. for C9H11O2: 151.0754, found: 151.0751.

1H NMR (500 MHz, CDCl3) δ = 7.89 (d, J = 8.6 Hz, 2H), 7.43 (d, J = 8.6 Hz, 2H), 2.59 (s, 3H).

13C NMR (126 MHz, CDCl3) δ = 196.85, 139.55, 135.41, 129.74, 128.88, 26.57.


1H NMR (500 MHz, CDCl3) δ = 7.87 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 2.59 (s, 3H),

2.42 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 197.91, 143.90, 134.70, 129.26, 128.46, 26.55, 21.65.


1H NMR (500 MHz, CDCl3) δ = 8.00 (dd, J = 8.7, 5.5 Hz, 2H), 7.15 (t, J = 8.6 Hz, 2H), 2.61 (s,

3H). 13

C NMR (126 MHz, CDCl3) δ = 196.54, 165.78 (d, J = 517.4 Hz), 133.58 (d, J = 3.0 Hz), 130.96

(d, J = 9.4 Hz), 115.68 (d, J = 21.4 Hz), 26.57. 19

F NMR (376 MHz, CDCl3) δ = -105.30 (s, 1F).

HRMS (ESI) (m/z): [M+H]+ calcd. for C8H8OF: 139.0554, found: 139.0551.


13C NMR (101 MHz, CDCl3) δ = 196.96, 139.65, 134.36 (q, J = 32.7 Hz), 128.60, 125.64 (q, J =

3.7 Hz), 123.59 (q, J = 272.7 Hz), 26.71. 19

F NMR (376 MHz, CDCl3) δ = -63.19 (s, 3F).


1H NMR (500 MHz, CDCl3) δ = 7.90 (td, J = 7.7, 1.8 Hz, 1H), 7.54 (tdd, J = 7.1, 5.1, 1.8 Hz, 1H),

7.24 (t, J = 7.5 Hz, 1H), 7.16 (dd, J = 11.1, 8.4 Hz, 1H), 2.67 (d, J = 4.9 Hz, 3H).

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13C NMR (126 MHz, CDCl3) δ = 196.02 (d, J = 3.3 Hz), 162.27 (d, J = 254.9 Hz), 134.72 (d, J =

9.1 Hz), 130.61 (d, J = 2.4 Hz), 125.71 (d, J = 12.7 Hz), 124.39 (d, J = 3.4 Hz), 116.68 (d, J =

23.8 Hz), 31.49 (d, J = 7.5 Hz). 19

F NMR (376 MHz, CDCl3) δ = -109.38 (m, 1F).


1H NMR (400 MHz, CDCl3) δ = 8.04 – 7.94 (m, 2H), 7.59 – 7.53 (m, 1H), 7.51 – 7.44 (m, 2H),

3.02 (q, J = 7.2 Hz, 2H), 1.24 (t, J = 7.2 Hz, 3H). 13

C NMR (101 MHz, CDCl3) δ = 200.85, 136.91, 132.90, 128.57, 127.98, 31.79, 8.24.


1H NMR (500 MHz, CDCl3) δ = 7.84 (dt, J = 8.4, 1.5 Hz, 4H), 7.64 – 7.59 (m, 2H), 7.54 – 7.48

(m, 4H). 13

C NMR (126 MHz, CDCl3) δ = 196.81, 137.61, 132.45, 130.09, 128.30.



13C NMR (126 MHz, CDCl3) δ = 194.50, 162.85, 132.25, 130.75, 113.47, 55.49.



2.46 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 192.70, 138.95, 136.48, 135.34, 130.06, 128.91, 127.27, 21.22.


1H NMR (500 MHz, CDCl3) δ = 9.96 (s, 1H), 7.51 (s, 2H), 7.28 (s, 1H), 2.41 (s, 6H).

13C NMR (126 MHz, CDCl3) δ = 192.87, 138.78, 136.58, 136.25, 127.59, 21.09.

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1H NMR (500 MHz, CDCl3) δ = 7.71 (d, J = 7.7 Hz, 1H), 7.38 (dd, J = 7.5, 1.3 Hz, 1H), 7.27

(ddd, J = 8.0, 7.6, 0.5 Hz, 2H), 2.59 (s, 3H), 2.55 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 201.74, 138.44, 137.61, 132.06, 131.55, 129.40, 125.72, 29.55,

21.63.


1H NMR (500 MHz, CDCl3) δ = 10.00 (s, 1H), 7.89 – 7.86 (m, 1H), 7.79 (d, J = 7.6 Hz, 1H), 7.63

(ddd, J = 7.9, 1.9, 1.0 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H). 13

C NMR (126 MHz, CDCl3) δ = 190.90, 137.81, 135.48, 134.43, 130.41, 129.33, 128.00.


1H NMR (500 MHz, CDCl3) δ = 10.03 (s, 1H), 7.94 – 7.86 (m, 2H), 7.68 – 7.61 (m, 1H), 7.54 (dd,

J = 10.7, 4.6 Hz, 2H). 13

C NMR (126 MHz, CDCl3) δ = 192.43, 136.39, 134.49, 129.75, 129.01.



2.45 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 192.06, 145.59, 134.19, 129.87, 129.73, 21.89.


1H NMR (500 MHz, CD3OD) δ = 9.78 (s, 1H), 7.80 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.6 Hz, 2H).

13C NMR (126 MHz, CD3OD) δ = 191.42, 163.78, 132.04, 128.90, 115.46.


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1H NMR (500 MHz, CDCl3) δ = 7.75 (d, J = 7.7 Hz, 1H), 7.58 (td, J = 7.6, 1.1 Hz, 1H), 7.51 –

7.45 (m, 1H), 7.39 – 7.32 (m, 1H), 3.17 – 3.10 (m, 2H), 2.71 – 2.65 (m, 2H). 13

C NMR (126 MHz, CDCl3) δ = 207.15, 155.20, 137.06, 134.63, 127.28, 126.73, 123.69, 36.22,

25.81.



3.91 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 190.91, 164.63, 132.03, 129.95, 114.33, 55.61.


1H NMR (500 MHz, CDCl3) δ = 9.98 (s, 1H), 7.49 – 7.43 (m, 2H), 7.40 (dd, J = 2.2, 1.0 Hz, 1H),

7.19 (dt, J = 6.8, 2.6 Hz, 1H), 3.87 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 192.19, 160.15, 137.80, 130.06, 123.57, 121.54, 112.04, 55.48.


1H NMR (500 MHz, CDCl3) δ = 10.00 (s, 1H), 7.77 (d, J = 8.5 Hz, 2H), 7.72 – 7.67 (m, 2H).

13C NMR (126 MHz, CDCl3) δ = 191.11, 135.07, 132.46, 131.00, 129.80.

HRMS (ESI) (m/z): [M+H]+ calcd. for C7H6OBr: 184.9597, found: 184.9596.

1H NMR (500 MHz, CDCl3) δ = 9.98 (s, 1H), 7.92 (dd, J = 8.8, 5.4 Hz, 2H), 7.22 (t, J = 8.5 Hz,

2H). 13

C NMR (126 MHz, CDCl3) δ = 190.55, 166.53 (J = 256.7 Hz), 132.97 (J = 2.7 Hz), 132.25 (J =

9.7 Hz), 116.37 (J = 22.3 Hz). 19

F NMR (376 MHz, CDCl3) δ = -102.42 (s, 1F).


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1H NMR (500 MHz, CDCl3) δ = 10.00 (s, 1H), 7.87 – 7.80 (m, 2H), 7.55 – 7.50 (m, 2H).

13C NMR (126 MHz, CDCl3) δ = 190.89, 140.95, 134.71, 130.93, 129.47.


1H NMR (500 MHz, CDCl3) δ = 9.94 (s, 1H), 8.14 (dd, J = 2.9, 1.2 Hz, 1H), 7.55 (dd, J = 5.1, 1.1

Hz, 1H), 7.39 (ddd, J = 5.1, 2.9, 0.8 Hz, 1H). 13

C NMR (126 MHz, CDCl3) δ = 185.02, 143.02, 136.83, 127.44, 125.34.

HRMS (ESI) (m/z): [M+H]+ calcd. for C5H5OS: 113.0056, found: 113.0058.

1H NMR (500 MHz, CDCl3) δ = 7.86 (d, J = 8.8 Hz, 2H), 7.80 – 7.75 (m, 2H), 7.62 – 7.56 (m,

1H), 7.50 (t, J = 7.6 Hz, 2H), 7.02 – 6.96 (m, 2H), 3.91 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 195.63, 163.24, 138.29, 132.60, 131.93, 130.16, 129.76, 128.22,

113.58, 55.53.


1H NMR (500 MHz, CDCl3) δ = 8.34 (dd, J = 7.9, 1.4 Hz, 2H), 7.76 – 7.70 (m, 2H), 7.50 (d, J =

8.4 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H). 13

C NMR (126 MHz, CDCl3) δ = 177.27, 156.20, 134.86, 126.76, 123.94, 121.86, 118.01.


1H NMR (500 MHz, CDCl3) δ = 7.79 (dd, J = 11.7, 5.0 Hz, 4H), 7.63 (t, J = 7.4 Hz, 1H), 7.56 –

7.43 (m, 4H). 13

C NMR (126 MHz, CDCl3) δ = 195.53, 138.92, 137.25, 135.87, 132.68, 131.50, 129.96, 128.66,

128.44.


S14

1H NMR (500 MHz, CDCl3) δ = 7.87 – 7.80 (m, 4H), 7.19 (t, J = 8.6 Hz, 4H).

13C NMR (126 MHz, CDCl3) δ = 193.85, 165.41 (d, J = 254.3 Hz), 133.70 (d, J = 3.1 Hz), 132.53

(d, J = 9.2 Hz), 115.58 (d, J = 21.9 Hz). 19

F NMR (376 MHz, CDCl3) δ = -105.74 (s, 2F).


1H NMR (500 MHz, CDCl3) δ = 7.67 (d, J = 7.3 Hz, 2H), 7.50 (dt, J = 14.7, 7.2 Hz, 4H), 7.34 –

7.27 (m, 2H). 13

C NMR (126 MHz, CDCl3) δ = 193.97, 144.44, 134.72, 134.14, 129.09, 124.32, 120.34.


1H NMR (500 MHz, CDCl3) δ = 7.55 (s, 1H), 7.41 (dd, J = 7.9, 1.0 Hz, 1H), 7.36 (d, J = 7.8 Hz,

1H), 3.12 – 3.06 (m, 2H), 2.71 – 2.66 (m, 2H), 2.40 (s, 3H). 13

C NMR (126 MHz, CDCl3) δ = 207.27, 152.58, 137.24, 137.22, 135.89, 126.37, 123.66, 36.59,

25.44, 21.09.



3.14 (dd, J = 13.1, 7.4 Hz, 2H), 2.69 (dd, J = 7.6, 4.3 Hz, 2H). 13

C NMR (126 MHz, CDCl3) δ = 205.64, 156.72, 135.94, 134.62, 130.97, 130.00, 124.95, 36.18,

25.56.

HRMS (ESI) (m/z): [M+H]+ calcd. for C9H8OBr: 210.9753, found: 210.9750.


1H), 6.93 (d, J = 7.9 Hz, 1H), 6.08 (s, 2H). 13

C NMR (126 MHz, CDCl3) δ = 190.36, 153.13, 148.71, 131.85, 128.73, 108.36, 106.86, 102.14.


S15


1H), 3.96 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 191.02, 151.83, 147.25, 129.82, 127.55, 114.49, 108.91, 56.11.


1H NMR (400 MHz, CD3CN) δ = 2.11 (s, 6H).

13C NMR (126 MHz, CD3CN) δ = 206.51, 29.91.

1H NMR (400 MHz, CD3CN) δ = 2.46 (q, J = 7.3 Hz, 2H), 2.09 (s, 3H), 0.98 (t, J = 7.3 Hz, 3H).

13C NMR (101 MHz, CD3CN) δ = 209.04, 36.07, 28.60, 7.11.

1H NMR (400 MHz, CD3CN) δ = 2.07 – 2.11 (m, 4H), 1.97 – 1.91 (m, 4H).

13C NMR (101 MHz, CD3CN) δ = 219.82, 37.73, 22.88.

1H NMR (400 MHz, CD3CN) δ = 2.30 (t, J = 6.6 Hz, 4H), 1.84 (dt, J = 12.4, 6.2 Hz, 4H), 1.75 –

1.69 (m, 2H). 13

C NMR (101 MHz, CD3CN) δ = 211.25, 41.47, 26.83, 24.63.

1H NMR (400 MHz, CD3CN) δ = 2.42 (t, J = 7.3 Hz, 2H), 2.08 (s, 3H), 1.60 – 1.49 (m, 2H), 0.90

(t, J = 7.4 Hz, 3H). 13

C NMR (101 MHz, CD3CN) δ = 208.66, 44.88, 28.97, 16.92, 12.94.

1H NMR (400 MHz, CD3CN) δ = 2.44 (q, J = 7.3 Hz, 4H), 0.99 (t, J = 7.3 Hz, 6H).

13C NMR (101 MHz, CD3CN) δ = 211.66, 34.81, 7.15.

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1H NMR (400 MHz, CD3CN) δ = 2.32 (d, J = 6.9 Hz, 2H), 2.11 – 2.04 (m, 4H), 0.92 (s, 3H), 0.90

(s, 3H). 13

C NMR (101 MHz, CD3CN) δ = 208.44, 51.99, 29.43, 24.23, 21.73.

1H NMR (400 MHz, CD3CN) δ = 2.62 (m, 1H), 2.11 (s, 3H), 1.07 (d, J = 7.0 Hz, 6H).

13C NMR (101 MHz, CD3CN) δ = 212.32, 41.08, 26.82, 17.41.

1H NMR (400 MHz, CD3CN) δ = 3.05 (t, J = 8.2 Hz, 4H), 1.98 (m, 2H).

13C NMR (101 MHz, CD3CN) δ = 209.15, 47.17, 9.20.

1H NMR (400 MHz, CD3CN) δ = 2.50 – 2.39 (m, 4H), 1.69 (m, 8H).

13C NMR (101 MHz, CD3CN) δ = 214.32, 43.41, 30.19, 24.06.

1H NMR (400 MHz, CD3CN) δ = 4.30 (t, J = 7.0 Hz, 2H), 2.43 (t, J = 8.0 Hz, 2H), 2.22 (dt, J =

15.0, 7.4 Hz, 2H). 13

C NMR (101 MHz, CD3CN) δ = 173.90, 68.54, 27.34, 21.81.

1H NMR (400 MHz, CD3CN) δ = 4.30 (t, J = 5.5 Hz, 2H), 2.49 (t, J = 6.9 Hz, 2H), 1.89 – 1.79 (m,

4H). 13

C NMR (101 MHz, CD3CN) δ = 171.40, 69.20, 29.44, 21.91, 18.67.

1H NMR (400 MHz, CD3CN) δ = 8.01 (dd, J = 7.8 Hz, 1.3 Hz, 1H), 7.61 (td, J = 7.6 Hz, 1.5 Hz,

1H), 7.47 – 7.41 (m, 1H), 7.37 (d, J = 7.7 Hz, 1H), 4.52 (t, J = 6.0 Hz, 2H), 3.08 (t, J = 6.0 Hz,

2H).

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13C NMR (101 MHz, CD3CN) δ = 169.35, 140.48, 133.65, 129.63, 127.58, 127.43, 67.45, 27.27.

1H NMR (400 MHz, CD3CN) δ = 2.43 (t, J = 7.4 Hz, 2H), 2.08 (s, 3H), 1.56 – 1.49 (m, 2H), 1.31

– 1.28 (m, 6H), 0.91 (t, J = 6.9 Hz, 3H). 13

C NMR (101 MHz, CD3CN) δ = 208.73, 42.99, 31.40, 28.96, 28.57, 23.50, 22.27, 13.35.

For hydrobenzoin, 1,2-bis(4-methylphenyl)ethane-1,2-diol, and 1,2-bis(4-chlorophenyl)-

ethane-1,2-diol, please refer to the Supplementary Information in RSC Adv. 2015, 5, 46026-46030.

For 1,2-bis(4-methoxyphenyl)ethane-1,2-diol, please refer to the Supplementary Information in

RSC Adv. 2012, 2, 11211-11214.

1H NMR (500 MHz, DMSO) δ = 12.48 (s, 1H), 8.14 (d, J = 7.7 Hz, 1H), 8.10 (d, J = 8.1 Hz, 2H),

7.83 (t, J = 7.1 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.51 (t, J = 7.5 Hz, 1H), 7.36 (d, J = 8.0 Hz, 2H),

2.39 (s, 3H). 13

C NMR (126 MHz, DMSO) δ = 162.76, 152.72, 149.30, 141.95, 135.07, 130.34, 129.67, 128.17,

127.89, 126.88, 126.32, 121.33, 21.47.

HRMS (ESI) (m/z): [M+H]+ calcd. for C15H13ON2: 237.1022, found: 237.1014.

1H NMR (500 MHz, DMSO) δ = 12.57 (s, 1H), 8.16 (d, J = 7.8 Hz, 1H), 7.88 – 7.82 (m, 1H),

7.80 (d, J = 7.8 Hz, 1H), 7.77 – 7.73 (m, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H),

7.15 (dd, J = 8.1 Hz, 2.2, 1H), 3.87 (s, 3H). 13

C NMR (126 MHz, DMSO) δ = 162.71, 159.81, 152.51, 149.12, 135.13, 134.47, 130.24, 128.02,

127.14, 126.33, 121.48, 120.60, 118.09, 112.99, 55.87.

HRMS (ESI) (m/z): [M+H]+ calcd. for C15H13O2N2: 253.0972, found: 253.0965.

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7.87 – 7.82 (m, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.62 – 7.50 (m, 4H). 13

C NMR (126 MHz, DMSO) δ = 162.78, 152.82, 149.22, 135.08, 133.17, 131.88, 129.08, 128.44,

128.11, 127.06, 126.87, 126.33, 121.42.



7.74 (d, J = 8.0 Hz, 1H), 7.51 (t, J = 7.5 Hz, 1H), 7.22 (s, 1H), 2.36 (s, 6H). 13

C NMR (126 MHz, DMSO) δ = 162.64, 152.92, 149.26, 138.23, 135.06, 133.2, 133.0, 127.92,

126.95, 126.31, 125.96, 121.42, 21.35.


1H NMR (500 MHz, DMSO) δ = 12.48 (s, 1H), 8.16 (d, J = 7.0 Hz, 1H), 8.03 (s, 1H), 7.98 (d, J =

7.4 Hz, 1H), 7.88 – 7.81 (m, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.52 (t, J = 7.4 Hz, 1H), 7.46 – 7.39 (m,

2H), 2.41 (s, 3H). 13

C NMR (126 MHz, DMSO) δ = 162.69, 152.85, 149.24, 138.39, 135.08, 133.10, 132.49, 128.98,

128.76, 127.95, 127.01, 126.32, 125.37, 121.44, 21.44.


1H NMR (500 MHz, DMSO) δ = 12.19 (s, 1H), 8.05 (d, J = 7.8 Hz, 1H), 7.75 (t, J = 7.6 Hz, 1H),

7.55 (d, J = 8.1 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 2.33 (s, 3H). 13

C NMR (126 MHz, DMSO) δ = 162.17, 154.71, 149.42, 134.72, 127.02, 126.30, 126.12, 121.07,

21.89.


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1H NMR (500 MHz, CDCl3) δ = 8.95 (d, J = 3.9 Hz, 1H), 8.20 (d, J = 8.2 Hz, 1H), 8.15 (d, J =

8.5 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.75 (t, J = 7.7 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.43 (dd, J

= 8.2, 4.2 Hz, 1H). 13

C NMR (126 MHz, CDCl3) δ = 150.33, 148.13, 136.26, 129.58, 129.33, 128.32, 127.82, 126.63,

121.11.

HRMS (ESI) (m/z): [M+H]+ calcd. for C9H8N: 130.0651, found: 130.0652.


7.27 (t, J = 7.2 Hz, 1H), 7.23 – 7.18 (m, 2H), 6.62 (s, 1H). 13

C NMR (126 MHz, CDCl3) δ = 135.80, 127.87, 124.21, 122.03, 120.79, 119.87, 111.09, 102.63.



7.86 (d, J = 8.2 Hz, 1H), 7.73 (t, J = 7.5 Hz, 1H), 7.69 (d, J = 5.7 Hz, 1H), 7.64 (t, J = 7.5 Hz,

1H). 13

C NMR (126 MHz, CDCl3) δ = 152.35, 142.60, 135.89, 130.56, 128.68, 127.75, 127.39, 126.51,

120.67.


1H NMR (400 MHz, CDCl3) δ = 8.03 (s, 1H), 7.49 (s, 1H), 7.32 (d, J = 8.3 Hz, 1H), 7.21 – 7.17

(m, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.53 –6.51 (m, 1H), 2.50 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 134.14, 129.03, 128.17, 124.25, 123.64, 120.37, 110.68, 102.13,

21.46.


1H NMR (400 MHz, CDCl3) δ = 8.08 (s, 1H), 7.31 (d, J = 8.8 Hz, 1H), 7.20 (t, J = 2.8 Hz, 1H),

7.15 (d, J = 2.3 Hz, 1H), 6.91 (dd, J = 8.8 Hz, 2.4, 1H), 6.52 (t, J = 2.1 Hz, 1H), 3.90 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 154.23, 130.99, 128.32, 124.89, 112.38, 111.73, 102.41, 102.37,

55.89.

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HRMS (ESI) (m/z): [M+H]+ calcd. for C9H10NO: 148.0757, found: 148.0756.

1H NMR (400 MHz, CDCl3) δ = 8.13 (s, 1H), 7.58 (d, J = 8.4 Hz, 1H), 7.41 (s, 1H), 7.24 – 7.20

(m, 1H), 7.13 (dd, J = 8.4, 1.8 Hz, 1H), 6.59 – 6.55 (m, 1H). 13

C NMR (101 MHz, CDCl3) δ = 136.15, 127.89, 126.46, 124.86, 121.58, 120.62, 110.98, 102.82.

HRMS (ESI) (m/z): [M+H]+ calcd. for C8H7NCl: 152.0262, found: 152.0262.


7.26 – 7.23 (m, 1H), 7.19 (dd, J = 8.6, 1.9 Hz, 1H), 6.56 – 6.51 (m, 1H). 13

C NMR (101 MHz, CDCl3) δ = 134.17, 128.99, 125.57, 125.50, 122.34, 120.14, 112.03, 102.44.


1H NMR (400 MHz, CDCl3) δ = 8.70 (s, 1H), 8.21 (s, 1H), 7.86 (dd, J = 8.4, 1.3 Hz, 1H), 7.70 (d,

J = 8.4 Hz, 1H), 7.39 (t, J = 2.8 Hz, 1H), 6.63 – 6.62 (m, 1H), 3.97 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 168.40, 135.19, 131.64, 127.68, 123.62, 120.84, 120.31, 113.58,

102.95, 52.00.

HRMS (ESI) (m/z): [M+H]+ calcd. for C10H10NO2: 176.0706, found: 176.0703.

1H NMR (500 MHz, CDCl3) δ = 8.79 (s, 1H), 8.64 (s, 1H), 8.14 (dd, J = 8.9, 1.7 Hz, 1H), 7.48 (d,

J = 9.0 Hz, 1H), 7.42 (s, 1H), 6.76 (s, 1H). 13

C NMR (126 MHz, CDCl3) δ = 141.89, 138.88, 127.51, 127.27, 118.06, 117.69, 111.14, 105.07.

HRMS (ESI) (m/z): [M+H]+ calcd. for C8H5N2O2: 161.0351, found: 161.0346.


7.58 (d, J = 5.8 Hz, 1H), 7.25 (dd, J = 9.0, 2.4 Hz, 1H), 7.08 (d, J = 2.3 Hz, 1H), 3.96 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 161.28, 151.37), 142.85), 138.01, 129.54, 124.47, 120.63,

120.05, 104.05, 55.53.


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1H NMR (400 MHz, CDCl3) δ = 7.73 (d, J = 7.9 Hz, 1H), 7.41 (dd, J = 8.2, 0.5 Hz, 1H), 7.34 –

7.29 (m, 1H), 7.24 – 7.18 (m, 1H), 7.12 (d, J = 3.1 Hz, 1H), 6.58 (dd, J = 3.1, 0.5 Hz, 1H), 3.85 (s,

3H). 13

C NMR (101 MHz, CDCl3) δ = 136.77, 128.85, 128.55, 121.54, 120.92, 119.33, 109.25, 100.95,

32.83.


1H NMR (400 MHz, CDCl3) δ = 8.04 (s, 1H), 7.60 (d, J = 7.8 Hz, 1H), 7.23 (t, J = 2.7 Hz, 1H),

7.16 – 7.12 (m, 1H), 7.10 – 7.08 (m, 1H), 6.65 –6.64 (m, 1H), 2.55 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 135.47, 127.43, 123.94, 122.53, 120.29, 120.07, 118.52, 103.12,

16.74.


1H NMR (400 MHz, CDCl3) δ = 8.47 (d, J = 8.1Hz, 1H), 7.63 – 7.55 (m, 1H), 7.42 – 7.36 (m,

2H), 7.33 – 7.28 (m, 1H), 6.65 (dd, J = 3.7, 0.6 Hz, 1H), 2.63 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 168.73, 135.56, 130.46, 125.29, 125.13, 123.69, 120.88, 116.56,

109.17, 23.98.


1H NMR (400 MHz, CDCl3) δ = 7.86 (s, 1H), 7.58 (d, J = 7.4 Hz, 1H), 7.31 – 7.28 (m, 1H), 7.20

– 7.10 (m, 2H), 6.27 (s, 1H), 2.46 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 136.09, 135.17, 129.09, 120.93, 119.64, 110.30, 100.36, 13.71.



1H), 7.25 – 7.18 (m, 4H), 6.68 – 6.64 (m, 1H), 5.39 (s, 2H). 13

C NMR (101 MHz, CDCl3) δ = 137.65, 136.41, 128.84, 128.37, 127.68, 126.87, 121.79, 121.08,

119.64, 109.81, 101.78, 50.14.

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1H NMR (400 MHz, CDCl3) δ = 8.01 (s, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.20 (s, 1H), 7.17 – 7.12

(m, 1H), 6.98 (d, J = 8.1 Hz, 1H), 6.52 (t, J = 2.1 Hz, 1H), 2.48 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 136.33, 131.78, 125.71, 123.61, 121.67, 120.39, 111.08, 102.36,

21.78.



7.40 – 7.32 (m, 1H), 7.30 – 7.28 (m, 1H), 7.20 (t, J = 7.3 Hz, 1H), 4.48 (q, J = 7.1 Hz, 2H), 1.47 (t,

J = 7.1 Hz, 3H). 13

C NMR (101 MHz, CDCl3) δ = 162.45, 137.11, 127.50, 125.33, 122.60, 120.76, 112.08, 108.70,

61.16, 14.43.


1H NMR (400 MHz, CDCl3) δ = 7.46 (s, 1H), 7.39 – 7.32 (m, 3H), 7.24 (d, J = 8.4 Hz, 1H), 7.19

– 7.15 (m, 3H), 7.08 (dd, J = 8.4, 1.3 Hz, 1H), 6.55 (dd, J = 3.1, 0.6 Hz, 1H), 5.35 (s, 2H). 13

C NMR (101 MHz, CDCl3) δ = 137.78, 134.79, 129.07, 128.79, 128.40, 127.58, 126.78, 123.37,

120.70, 109.46, 101.17, 50.16, 21.47.



5H), 6.54 (d, J = 3.0 Hz, 1H), 5.33 (s, 2H). 13

C NMR (101 MHz, CDCl3) δ = 137.13, 134.75, 129.8, 129.7, 128.89, 127.83, 126.74, 125.36,

122.05, 120.39, 110.80, 101.40, 50.34.


1H NMR (400 MHz, CDCl3) δ = 7.70 (d, J = 7.7 Hz, 1H), 7.35 (dd, J = 8.2, 0.5 Hz, 1H), 7.25 –

7.20 (m, 1H), 7.18 – 7.10 (m, 4H), 6.91 – 6.84 (m, 2H), 6.59 (dd, J = 3.1, 0.6 Hz, 1H), 5.29 (s,

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2H), 3.81 (s, 3H). 13

C NMR (101 MHz, CDCl3) δ = 159.12, 136.28, 129.57, 128.79, 128.25, 128.12, 121.64, 120.99,

119.50, 114.17, 109.73, 101.56, 55.30, 49.61.


1H NMR (400 MHz, CDCl3) δ = 8.01 (d, J = 8.3 Hz, 1H), 7.52 (d, J = 7.6 Hz, 1H), 7.34 – 7.29 (m,

1H), 7.25 – 7.21 (m, 1H), 6.60 (s, 1H), 4.83 (s, 2H), 1.74 (s, 9H). 13

C NMR (101 MHz, CDCl3) δ = 155.07, 140.25, 124.46, 123.09, 120.92, 115.67, 109.78, 85.14,

58.95, 28.27.


1H NMR (400 MHz, CDCl3) δ = 8.15 – 8.10 (m, 3H), 7.92 (ddd, J = 7.8, 1.1, 0.5 Hz, 1H), 7.55 –

7.49 (m, 4H), 7.41 (ddd, J = 8.2, 7.4, 1.2 Hz, 1H). 13

C NMR (101 MHz, CDCl3) δ = 168.10, 154.17, 135.09, 133.65, 131.00, 129.05, 127.59, 126.35,

125.22, 123.27, 121.65.

HRMS (ESI) (m/z): [M+H]+ calcd. for C13H10NS: 212.0528, found: 212.0524.


2H), 7.18 – 7.09 (m, 4H), 6.60 (d, J =3.1 Hz, 1H), 5.71 (q, J = 7.1 Hz, 1H), 1.95 (d, J = 7.1 Hz,

3H). 13

C NMR (126 MHz, CDCl3) δ = 142.73, 136.08, 128.77, 128.71, 127.44, 125.93, 124.89, 121.46,

120.91, 119.55, 110.07, 101.46, 54.81, 21.78.


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NMR spectra

1H NMR spectrum of product b1 in CDCl3

13C NMR spectrum of product b1 in CDCl3

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19F NMR spectrum of product b6 in CDCl3


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1H NMR spectrum of product b32 in CD3OD

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13C NMR spectrum of product b32 in CD3OD


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1H NMR spectrum of product b39 in CD3CN in the reaction NMR tube

13C NMR spectrum of product b39 in CD3CN in the reaction NMR tube

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1H NMR spectrum of product b54 in d6-DMSO

13C NMR spectrum of product b54 in d6-DMSO

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1H NMR spectrum of product d1 in CDCl3

13C NMR spectrum of product d1 in CDCl3

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1H NMR spectrum of Markovnikov hydroamination product in CDCl3

13C NMR spectrum of Markovnikov hydroamination product in CDCl3

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31P NMR spectrum of Ptpop-I in D2O

1H NMR spectrum of Ptpop-II in CD3OD

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31P NMR spectrum of Ptpop-II in CD3OD

31P NMR spectrum of Ptpop-III in CD3OD

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19F NMR spectrum of Ptpop-BF2-IV in CD3CN

31P NMR spectrum of Ptpop-BF2-IV in CD3CN

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Investigation of kinetic isotopic effect on photo-dehydrogenation of alcohols

Investigation of kinetic isotopic effect on photo-dehydrogenation of alcohols

electronic supplementary information · 2019. 4. 1. · (p 2 o 5 h 2) 4], ptpop-iii: ptpop-i (225...

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