S1

Supporting Information

Conformation controlled stepwise hydride shuffling from

the metal to the ligand backbone

Nicholas R. Wiedmaier, Hansjörg Speth, Georg Leistikow, Klaus Eichele, Hartmut Schubert,

Hermann A. Mayer*, Lars Wesemann*

Content Crystallographic Details .............................................................................................. 2

NMR data ................................................................................................................... 4

1H NMR spectrum of compound 2 ........................................................................... 4

13C{1H} NMR spectrum of compound 2 ................................................................... 5

31P{1H} NMR spectrum of compound 2 ................................................................... 6

1H NMR spectrum of compound 3 ........................................................................... 7

13C{1H} NMR spectrum of compound 3 ................................................................... 8

19F{1H} NMR spectrum of compound 3 ................................................................... 9

31P{1H} NMR spectrum of compound 3 ................................................................. 10

1H NMR spectrum of 4 .......................................................................................... 11

13C{1H} NMR spectrum of 4 ................................................................................... 12

31P{1H} NMR spectrum of 4 ................................................................................... 13

1H NMR spectrum of compound 5 ......................................................................... 14

13C{1H} NMR spectrum of compound 5 ................................................................. 15

19F{1H} NMR spectrum of compound 5 ................................................................. 16

31P{1H} NMR spectrum of compound 5 ................................................................. 17

1H NMR spectrum of 6 .......................................................................................... 18

13C {1H} NMR spectrum of 6 .................................................................................. 19

31P{1H} NMR spectrum of 6 ................................................................................... 20

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2020

S2

Crystallographic Details

Table 1S. Selected crystallographic data for compound 2, 3.

syn-2 3 Empirical formula C31H48O2P2Ru

C32H51BCl2F4O2P2Ru [C31H49O2P2Ru] BF4 × CH2Cl2

M [g·mol–1] 615.70 788.45 [Å] 0.71073 0.71073

100(2) 100(2) Crystal system triklin monoklin Space group P1̅ P21/c Z 2 4 a [Å] 11.7759(2) 11.9110(3) b [Å] 12.0484(2) 12.8598(3) c [Å] 13.1386(2) 23.6570(5) 100.4810 (10) 90

106.2420(10) 98.8350(10)

117.2990(10) 90 V [Å3] 1481.55(4) 3580.62(14) Dc [g·cm–3] 1.380 1.463 [mm–1] 0.663 0.725 F(000) 948 1632 Crystal size [mm] 0.26 x 0.13 x 0.10 0.11 x 0.15 x 0.17 range [°] 2.56 – 27.14 2.35 – 29.15 Limiting indices –15 ≤ h ≤ 15

–15 ≤ k ≤ 15 –16 ≤ l ≤ 16

–16 ≤ h ≤ 16 –17 ≤ k ≤ 17 –32 ≤ l ≤ 32

Reflections collected

14133 140096

Independent 13333 9631 Rint 0.0218 0.0248 Completeness 99.9 99.6 Absorption correction

Numerisch multi-scan

Max. , Min. 0.935, 0.844 0.7458, 0.6860 Parameters/ restraints

345/ 0 417/ 1

R1, wR2 [I>] 0.0201, 0.0473 0.0360, 0.0766 R1, wR2 (all data) 0.0239, 0.0488 0.0380, 0.0775 GooF on F2 1.039 1.253 Peak/ hole [e·Å–3] 0.442, –0.414 0.785, –0.709 CCDC 1982522 1982525

S3 Table 2S. Selected crystallographic data for compound 5, 6.

5 syn-6 Empirical formula C67H63BF24O2P2Ru

[C31H51O2P2Ru]C36H12BF24 C33H56O2.5P2Ru C31H52O2P2Ru x 0.5 THF

M [g·mol–1] 1481.86 655.78 [Å] 0.71073 0.71073

100(2) 100(2) Crystal system monoklin monoklin Space group P21/n P21/c Z 8 4 a [Å] 12.9706(3) 10.5466(8) b [Å] 16.5597(3) 11.6310(8) c [Å] 31.8663(7) 27.2772(19) 90 90

99.5240(10) 98.329(3)

90 90 V [Å3] 6750.2(2) 3310.7(4) Dc [g·cm–3] 1.458 1.316 [mm–1] 0.387 0.599 F(000) 3008 1392 Crystal size [mm] 0.18 x 0.16 x 0.14 0.20 x 0.19 x 0.17 range [°] 2.46 – 28.67 3.82 – 27.88 Limiting indices –17 ≤ h ≤ 14

–22 ≤ k ≤ 22 –36 ≤ l ≤ 43

–13 ≤ h ≤ 9 –15 ≤ k ≤ 14 –35 ≤ l ≤ 35

Reflections collected

107737 21639

Independent 17376 7811 Rint 0.0310 0.0175 Completeness 99.8 98.7 Absorption correction

multi-scan multi-scan

Max. , Min. 0.7458, 0.6940 0.7456, 0.7044 Parameters/ restraints

882/ 0 362/ 8

R1, wR2 [I>] 0.0418, 0.1026 0.0251, 0.0564 R1, wR2 (all data) 0.0532, 0.1098 0.0297, 0.0584 GooF on F2 1.028 1.026 Peak/ hole [e·Å–3] 1.675, –1.348 0.634, –0.957 CCDC 1982524 1982523

S4

NMR data 1H NMR spectrum of compound 2

-6-5-4-3-2-18 7 6 5 4 3 2 1 0 ppm

-7.0

4-7

.03

-6.9

8-6

.98

1.1

61

.18

1.1

91

.24

1.2

51

.27

1.8

41

.85

1.8

71

.87

1.8

91

.90

2.1

52

.16

2.1

72

.19

2.1

92

.20

3.1

95

.15

5.1

66

.67

6.6

86

.68

6.6

96

.78

6.7

96

.79

1.0

5

18

.10

18

.28

2.1

02

.09

1.0

5

2.0

7

2.1

11

.99

1H_NMR_C6D6_BCHT-PtBu2-Ru(CO)2H Current Data ParametersNAME GL1-060618-NachtEXPNO 10PROCNO 1

F2 - Acquisition ParametersDate_ 20180606Time 20.04INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zg30TD 52656SOLVENT C6D6NS 32DS 0SWH 12019.230 HzFIDRES 0.228259 HzAQ 2.1904895 secRG 161DW 41.600 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.60 usecPL1 -3.00 dBPL1W 16.03799057 WSFO1 400.1100000 MHz

F2 - Processing parametersSI 65536SF 400.1099934 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00

# C6D6

#

THF

THF

S5

13C{1H} NMR spectrum of compound 2

200 180 160 140 120 100 80 60 40 20 ppm

30

.13

0.5

30

.53

0.6

35

.93

6.0

36

.13

7.3

37

.43

7.5

37

.83

7.9

37

.93

8.6

67

.8

12

2.0

12

2.1

12

2.2

12

6.7

13

0.8

13

7.4

14

9.2

14

9.2

14

9.3

20

3.6

20

3.7

20

3.8

20

6.0

Current Data ParametersNAME GL1-060618-Nacht_2EXPNO 16PROCNO 1

F2 - Acquisition ParametersDate_ 20180607Time 7.18INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 53700SOLVENT C6D6NS 15000DS 0SWH 30864.197 HzFIDRES 0.574752 HzAQ 0.8699400 secRG 32800DW 16.200 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 13.50 usecPL1 -4.16 dBPL1W 78.55633545 WSFO1 100.6198135 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 65536SF 100.6077005 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

13C_ BCHT-PtBu2-Ru(CO)2HNMR_C6D6_

# C6D6

#

204205206 ppm

20

3.6

20

3.7

20

3.8

20

6.0

353637383940 ppm

35.9

36.0

36.1

37.3

37.4

37.5

37.8

37.9

37.9

38.6

S6

31P{1H} NMR spectrum of compound 2

-150-100-50150 100 50 0 ppm

91.2

31P_NMR_C6D6_BCHT-PtBu2-Ru(CO)2HCurrent Data ParametersNAME GL1-060618-NachtEXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20180606Time 20.07INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 88150SOLVENT C6D6NS 64DS 0SWH 65789.477 HzFIDRES 0.746336 HzAQ 0.6699400 secRG 23100DW 7.600 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 31PP1 11.00 usecPL1 -3.00 dBPL1W 45.10684967 WSFO1 161.9674970 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 161.9674970 MHzWDW EMSSB 0LB 3.00 HzGB 0PC 1.40

S7

1H NMR spectrum of compound 3

-19 8 7 6 5 4 3 2 1 0 ppm1.1

21.1

51.2

01.2

31.3

51.3

91.4

21.4

52.0

52.0

52.0

72.0

72.5

32.5

42.6

02.6

02.6

32.9

33.1

63.1

73.1

83.1

93.1

93.2

13.2

63.3

06.3

86.3

86.3

97.0

97.1

17.1

57.1

67.1

77.1

87.1

97.2

07.2

07.5

77.7

37.7

37.7

4

9.2

89.0

29.7

89.6

6

1.0

41.0

32.0

91.0

22.0

21.1

4

1.0

0

4.0

9

4.5

09.9

4

Current Data ParametersNAME NW53-130718-NachtEXPNO 10PROCNO 1

F2 - Acquisition ParametersDate_ 20180713Time 20.05INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zg30TD 52656SOLVENT CD2Cl2NS 16DS 0SWH 16025.641 HzFIDRES 0.304346 HzAQ 1.6428672 secRG 228DW 31.200 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.60 usecPL1 -3.00 dBPL1W 16.03799057 WSFO1 400.1100000 MHz

F2 - Processing parametersSI 65536SF 400.1100114 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00

1H_ (BCHD-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

# CD2Cl2

#

7.17.2 ppm

7.0

97

.11

7.1

47

.15

7.1

67

.17

7.1

87

.19

7.2

07

.20

4.0

9

2.53.0 ppm

2.0

72.0

72.5

32.5

42.6

02.6

02.6

33.1

63.1

73.1

83.1

93.1

93.2

13.2

63.3

0

1.0

4

1.0

32

.09

1.0

2

2.0

21

.14

S8

13C{1H} NMR spectrum of compound 3

200 180 160 140 120 100 80 60 40 20 ppm1

4.3

29

.12

9.1

29

.22

9.2

29

.52

9.6

30

.93

1.1

36

.93

7.1

43

.14

3.3

86

.211

7.9

11

7.9

11

7.9

12

0.5

12

1.0

12

3.7

12

5.1

12

5.3

12

6.4

12

7.1

12

7.7

12

9.0

12

9.1

12

9.1

12

9.2

12

9.2

12

9.4

12

9.5

12

9.5

12

9.5

13

1.8

13

1.8

13

5.2

13

9.4

16

1.5

16

1.9

16

2.4

16

2.9

13C_ (BCHD-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

Current Data ParametersNAME NW53-130718-NachtEXPNO 17PROCNO 1

F2 - Acquisition ParametersDate_ 20180714Time 7.18INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 53700SOLVENT CD2Cl2NS 15000DS 0SWH 30864.197 HzFIDRES 0.574752 HzAQ 0.8699400 secRG 32800DW 16.200 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 13.50 usecPL1 -4.16 dBPL1W 78.55633545 WSFO1 100.6198135 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 65536SF 100.6076933 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

196197198 ppm

195

.41

95

.51

95

.6

198

.41

98

.5

120125130135 ppm

117

.9117

.9117

.91

20.5

12

1.0

12

3.7

12

5.1

12

5.3

12

6.4

12

7.1

12

7.7

12

9.0

12

9.1

12

9.1

12

9.2

12

9.2

12

9.4

12

9.5

12

9.5

12

9.5

12

9.8

13

1.8

13

1.8

13

5.2

13

9.4

38404244 ppm

36.9

37.1

37.1

37.6

37.6

37.7

39.0

43.1

43.3

## CD2Cl2

S9

19F{1H} NMR spectrum of compound 3

-200-150-100-500 ppm

-62

.8

Current Data ParametersNAME NW53-130718-NachtEXPNO 12PROCNO 1

F2 - Acquisition ParametersDate_ 20180713Time 20.07INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgfhigqnTD 131072SOLVENT CD2Cl2NS 32DS 0SWH 100000.000 HzFIDRES 0.762939 HzAQ 0.6553600 secRG 4100DW 5.000 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 18.75 usecPL1 -2.92 dBPL1W 30.50645256 WSFO1 376.4306030 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL2W 16.03799057 WPL12W 0.53474891 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 262144SF 376.4795470 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00

19F_ (BCHD-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

S10

31P{1H} NMR spectrum of compound 3

-150-100-50150 100 50 0 ppm

74.7

75.8

79.4

80.5

31P_ (BCHD-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

Current Data ParametersNAME NW53-130718-NachtEXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20180713Time 20.06INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 88150SOLVENT CD2Cl2NS 32DS 0SWH 65789.477 HzFIDRES 0.746336 HzAQ 0.6699400 secRG 23100DW 7.600 usecDE 6.00 usecTE 300.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 31PP1 11.00 usecPL1 -3.00 dBPL1W 45.10684967 WSFO1 161.9674970 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 161.9674970 MHzWDW EMSSB 0LB 3.00 HzGB 0PC 1.40

76788082 ppm

74

.7

75

.8

79

.4

80

.5

S11

1H NMR spectrum of 4

Current Data ParametersNAME NW103-29112018-600-NachtEXPNO 10PROCNO 1

F2 - Acquisition ParametersDate_ 20181129Time 14.30 hINSTRUM spectPROBHD Z126545_0027 (PULPROG zg30TD 65536SOLVENT C6D6NS 64DS 0SWH 9615.385 HzFIDRES 0.293438 HzAQ 3.4078720 secRG 17.08DW 52.000 usecDE 10.00 usecTE 298.0 KD1 1.00000000 secTD0 1SFO1 600.1300000 MHzNUC1 1HP1 12.00 usecPLW1 23.41200066 W

F2 - Processing parametersSI 65536SF 600.1299951 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

1H_ BCHD-PtBu2-Ru(CO)2HNMR_C6D6_

-6-5-4-3-2-17 6 5 4 3 2 1 0 ppm

-6.9

10.9

60.9

81.0

81.0

91.1

21.2

11.2

21.2

31.2

41.2

51.2

61.2

71.2

91.3

21.5

11.5

21.9

52.5

12.5

22.6

42.6

42.7

72.7

92.8

13.1

33.1

55.9

35.9

35.9

37.0

57.0

77.1

07.1

27.1

37.1

57.1

97.2

67.2

7

0.5

11

.02

4.4

79

.60

31

.79

9.1

01

.16

0.4

61

.05

1.0

40

.45

1.5

11

.05

0.5

22

.04

0.5

10

.52

1.0

60

.45

0.4

41

.00

1.5

33

.08

0.5

11

.12

# C6D6

-7.0 ppm

-7.2

4-7

.20

-6.9

5-6

.95

-6.9

1-6

.88

7.2 ppm

7.0

57

.07

7.1

07

.12

7.1

37

.15

7.2

67

.27

1.61.82.02.22.42.62.83.03.2 ppm

1.4

91.5

01.5

11.5

21.5

31.5

41.9

31.9

41.9

41.9

51.9

61.9

72.2

92.2

92.3

02.4

82.5

02.5

12.5

22.6

22.6

42.6

42.6

62.7

72.7

92.8

02.8

12.8

22.9

22.9

33.0

03.1

33.1

5

1.1

6

0.4

6

1.0

5

1.0

4

0.4

5

1.5

1

1.0

5

0.5

2

2.0

4

0.5

1

0.5

2

1.0

6

0.4

5

#

S12

13C{1H} NMR spectrum of 4

200 180 160 140 120 100 80 60 40 20 ppm29

.829

.830

.030

.030

.130

.130

.130

.230

.330

.330

.430

.730

.730

.932

.732

.934

.234

.435

.737

.439

.739

.945

.445

.648

.152

.552

.552

.652

.611

8.8

118

.912

4.7

12

5.1

12

6.1

12

6.3

12

8.8

12

9.2

13

0.1

13

1.0

13

8.2

13

8.2

14

0.1

Current Data ParametersNAME NW103-29112018-600-NachtEXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20181129Time 18.36 hINSTRUM spectPROBHD Z126545_0027 (PULPROG udeftTD 25902SOLVENT C6D6NS 3072DS 0SWH 36231.883 HzFIDRES 2.797613 HzAQ 0.3574476 secRG 189.6DW 13.800 usecDE 18.00 usecTE 298.0 KD1 4.00000000 secD12 0.00002000 secD20 25.00000000 secTD0 1SFO1 150.9178988 MHzNUC1 13CP1 10.00 usecP13 2000.00 usecP26 500.00 usecPLW1 57.02700043 WSPNAM[5] Crp60comp.4SPOAL5 0.500SPOFFS5 0 HzSPW5 8.71310043 WSPNAM[8] Crp60,0.5,20.1SPOAL8 0.500SPOFFS8 0 HzSPW8 8.71310043 WSFO2 600.1300000 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 70.00 usecPLW2 23.41200066 WPLW12 0.68803000 W

F2 - Processing parametersSI 32768SF 150.9027515 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

13C_ BCHD-PtBu2-Ru(CO)2HNMR_C6D6_

# C6D6 #

204205206207208 ppm

20

3.1

20

3.6

20

3.6

20

3.7

20

6.6

20

6.7

20

6.7

20

8.0

20

8.1

363840424446485052 ppm

32

.73

2.9

34

.23

4.4

35

.63

5.7

35

.73

6.8

36

.93

7.4

37

.53

9.7

39

.94

2.3

42

.44

5.4

45

.64

7.4

48

.15

2.5

52

.55

2.6

52

.6120125130135 ppm

118

.811

8.9

124

.71

25

.11

26

.11

26

.31

28

.81

29

.21

30

.11

31

.0

137

.21

38

.21

38

.21

39

.2

S13

31P{1H} NMR spectrum of 4

-150-100-50150 100 50 0 ppm

87

.18

8.4

90

.89

1.2

91

.79

2.0

92

.29

3.0

93

.51

03.0

10

4.2

Current Data ParametersNAME NW103-231118-1EXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20181123Time 15.31INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 88150SOLVENT C6D6NS 64DS 0SWH 65789.477 HzFIDRES 0.746336 HzAQ 0.6699400 secRG 23100DW 7.600 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 31PP1 11.00 usecPL1 -3.00 dBPL1W 45.10684967 WSFO1 161.9674970 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 161.9674970 MHzWDW EMSSB 0LB 3.00 HzGB 0PC 1.40

31P_ BCHD-PtBu2-Ru(CO)2HNMR_C6D6_

86889092949698100102104 ppm

87

.1

88

.4

90

.891

.291

.792

.092

.293

.093

.5

10

3.0

10

4.2

S14

1H NMR spectrum of compound 5

Current Data ParametersNAME NW88-041218-NachtEXPNO 10PROCNO 1

F2 - Acquisition ParametersDate_ 20181204Time 20.12INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zg30TD 52656SOLVENT CD2Cl2NS 64DS 0SWH 4000.000 HzFIDRES 0.075965 HzAQ 6.5819998 secRG 228DW 125.000 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.60 usecPL1 -3.00 dBPL1W 16.03799057 WSFO1 400.1120006 MHz

F2 - Processing parametersSI 65536SF 400.1100000 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00

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 ppm1

.14

1.1

51

.17

1.1

71

.40

1.4

11

.43

2.0

62

.07

2.0

92

.10

2.1

22

.15

2.1

62

.17

2.1

92

.22

2.2

32

.46

2.4

72

.49

2.5

02

.51

2.5

52

.58

2.5

92

.60

2.6

12

.63

2.6

43

.00

3.0

33

.04

3.0

63

.20

3.2

37

.19

7.6

07

.75

7.7

67

.77

18

.09

18

.67

1.0

71

.99

2.0

42

.04

2.0

02

.00

4.0

4

4.1

68

.86

1H_ (BCH-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

2.42.62.83.03.2 ppm

2.0

92

.10

2.1

22

.19

2.2

32

.49

2.5

02

.51

2.5

92

.60

2.6

32

.64

3.0

03

.03

3.0

43

.06

3.2

03

.23

1.0

7

1.9

9

2.0

4

2.0

4

2.0

0

2.0

0

#

# CD2Cl2

S15

13C{1H} NMR spectrum of compound 5

200 180 160 140 120 100 80 60 40 20 ppm

29

.22

9.2

30

.13

4.8

34

.93

5.0

37

.53

7.6

37

.73

7.8

43

.54

3.6

43

.75

1.6

51

.76

6.1

87

.1

11

7.9

11

7.9

11

7.9

12

1.0

12

3.7

12

6.4

12

7.4

12

8.7

12

8.8

12

9.1

12

9.2

12

9.4

12

9.5

12

9.8

13

5.2

14

0.6

16

1.4

16

1.9

16

2.4

16

2.9

19

5.1

19

9.6

19

9.7

13C_ (BCH-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

Current Data ParametersNAME NW88-091218-Nacht_2EXPNO 14PROCNO 1

F2 - Acquisition ParametersDate_ 20181210Time 7.47INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG udeftTD 22218SOLVENT CD2Cl2NS 11300DS 0SWH 30864.197 HzFIDRES 1.389153 HzAQ 0.3599316 secRG 32800DW 16.200 usecDE 6.00 usecTE 299.2 KD1 3.00000000 secD11 0.03000000 secD12 0.00002000 secD20 100.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 13.50 usecP13 2000.00 usecP26 500.00 usecPL1 -4.16 dBPL1W 78.55633545 WSFO1 100.6198135 MHzSP8 1.39 dBSP13 1.39 dBSPNAM[8] Crp60,0.5,20.1SPNAM[13 Crp60comp.4SPOAL8 0.500SPOAL13 0.500SPOFFS8 0 HzSPOFFS13 0 Hz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL2W 16.03799057 WPL12W 0.53474891 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 100.6076941 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.40

196198200 ppm

19

5.1

19

9.6

19

9.7

# CD2Cl2

#

363840424446485052 ppm

34

.93

5.0

37

.53

7.6

37

.73

7.8

43

.54

3.6

43

.7

51

.65

1.7

S16

19F{1H} NMR spectrum of compound 5

-200-150-100-500 ppm

-62

.8

Current Data ParametersNAME NW88-041218-NachtEXPNO 18PROCNO 1

F2 - Acquisition ParametersDate_ 20180903Time 16.11INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgfhigqnTD 131072SOLVENT CD2Cl2NS 32DS 0SWH 100000.000 HzFIDRES 0.762939 HzAQ 0.6553600 secRG 4100DW 5.000 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 18.75 usecPL1 -2.92 dBPL1W 30.50645256 WSFO1 376.4306030 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL2W 16.03799057 WPL12W 0.53474891 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 262144SF 376.4795470 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00

19F_ (BCH-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

S17

31P{1H} NMR spectrum of compound 5

-150-100-50150 100 50 0 ppm

78

.1

Current Data ParametersNAME NW88-041218-NachtEXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20181204Time 20.14INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 88150SOLVENT CD2Cl2NS 64DS 0SWH 65789.477 HzFIDRES 0.746336 HzAQ 0.6699400 secRG 23100DW 7.600 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 31PP1 11.00 usecPL1 -3.00 dBPL1W 45.10684967 WSFO1 161.9674970 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 161.9674970 MHzWDW EMSSB 0LB 3.00 HzGB 0PC 1.40

31P_ (BCH-PtBu2-Ru(CO)2)BArF24NMR_CD2Cl2_

S18

1H NMR spectrum of 6

1H_ BCH-PtBu2-Ru(CO)2HNMR_C6D6_Current Data ParametersNAME NW159-131218-NachtEXPNO 10PROCNO 1

F2 - Acquisition ParametersDate_ 20181213Time 20.06INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zg30TD 52656SOLVENT C6D6NS 32DS 0SWH 8305.647 HzFIDRES 0.157734 HzAQ 3.1698911 secRG 161DW 60.200 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.60 usecPL1 -3.00 dBPL1W 16.03799057 WSFO1 400.1100000 MHz

F2 - Processing parametersSI 65536SF 400.1099924 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00

#

# C6D6

-7.0 ppm

-7.3

3-7

.32

-7.2

8-7

.27

-7.1

2-7

.06

-7.0

1

1.0

0

2.02.53.0 ppm

1.6

41.6

82.0

22.0

52.0

62.1

22.1

32.1

52.1

62.7

92.8

23.0

03.0

3

2.0

2

1.0

1

3.9

8

1.9

5

1.9

3

-6-5-4-3-2-17 6 5 4 3 2 1 0 ppm-7

.06

1.2

01

.21

1.2

31

.26

1.2

81

.29

1.6

01

.61

1.6

21

.64

1.6

71

.68

1.6

91

.84

2.0

22

.03

2.0

52

.06

2.0

92

.12

2.1

32

.14

2.1

52

.16

2.1

92

.76

2.7

92

.82

3.0

03

.03

3.0

63

.10

7.0

77

.07

7.0

87

.09

7.1

07

.11

7.1

27

.13

7.1

4

1.0

0

18

.03

17

.95

2.0

21

.01

3.9

81

.95

1.9

3

3.9

8

S19

13C {1H} NMR spectrum of 6

200 180 160 140 120 100 80 60 40 20 ppm

30

.23

0.4

30

.43

5.6

35

.73

5.8

36

.83

6.8

36

.93

8.0

45

.55

1.9

54

.9

12

6.4

12

9.1

14

2.6

20

3.6

20

3.7

Current Data ParametersNAME NW159-131218-Nacht_2EXPNO 13PROCNO 1

F2 - Acquisition ParametersDate_ 20181214Time 4.55INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG udeftTD 22218SOLVENT C6D6NS 7500DS 0SWH 30864.197 HzFIDRES 1.389153 HzAQ 0.3599316 secRG 32800DW 16.200 usecDE 6.00 usecTE 299.2 KD1 3.00000000 secD11 0.03000000 secD12 0.00002000 secD20 100.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 13.50 usecP13 2000.00 usecP26 500.00 usecPL1 -4.16 dBPL1W 78.55633545 WSFO1 100.6198135 MHzSP8 1.39 dBSP13 1.39 dBSPNAM[8] Crp60,0.5,20.1SPNAM[13 Crp60comp.4SPOAL8 0.500SPOAL13 0.500SPOFFS8 0 HzSPOFFS13 0 Hz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL2W 16.03799057 WPL12W 0.53474891 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 100.6077013 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.40

13C_ BCH-PtBu2-Ru(CO)2HNMR_C6D6_

## C6D6

204206208 ppm

203

.62

03

.7

208

.5

384042444648505254 ppm

35

.83

6.8

36

.83

6.9

38

.0

45

.5

51

.9

54

.9

S20

31P{1H} NMR spectrum of 6

-150-100-50150 100 50 0 ppm

92

.094

.3

Current Data ParametersNAME NW159-131218-NachtEXPNO 11PROCNO 1

F2 - Acquisition ParametersDate_ 20181213Time 20.08INSTRUM spectPROBHD 5 mm QNP 1H/13PULPROG zgpg30TD 88150SOLVENT C6D6NS 64DS 0SWH 65789.477 HzFIDRES 0.746336 HzAQ 0.6699400 secRG 23100DW 7.600 usecDE 6.00 usecTE 299.2 KD1 1.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 31PP1 11.00 usecPL1 -3.00 dBPL1W 45.10684967 WSFO1 161.9674970 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 11.77 dBPL13 13.14 dBPL2W 16.03799057 WPL12W 0.53474891 WPL13W 0.39007664 WSFO2 400.1120007 MHz

F2 - Processing parametersSI 131072SF 161.9674970 MHzWDW EMSSB 0LB 3.00 HzGB 0PC 1.40

31P_ BCH-PtBu2-Ru(CO)2HNMR_C6D6_