Supporting information for Antitumoral Ruthenium(II) Arene ... · Crystal size 0.15 x 0.15 x 0.10 mm3 Theta range for data collection 4.037 to 68.287°. Index ranges -11

S1

Supporting information for

Aminophosphine Ligands as a Privileged Platform for Development of Antitumoral Ruthenium(II) Arene Complexes

Lewis Marc Broomfield,[a] Carlos Alonso-Moreno, * [b] Eddy Martin,[a] Alexandr Shafir,*[a]

Inmaculada Posadas,*[c,d] Valentín Ceña,[c,e] José A. Castro-Osma[b]

[a] Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain

[b] Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Farmacia, Universidad de Castilla-La Mancha, Campus Universitario, 02071-Albacete, Spain.

[c] CIBERNED, Instituto de Salud Carlos III, Madrid, Spain.

[d] Unidad Asociada Neurodeath CSIC-UCLM, Departamento de Ciencias Médicas, Facultad de Farmacia, Universidad de Castilla-La Mancha, Campus Universitario de Albacete, 02071-Albacete, Spain.

[e] Unidad Asociada Neurodeath CSIC-UCLM, Departamento de Ciencias Médicas, Facultad de Medicina, Universidad de Castilla-La Mancha, Campus Universitario de Albacete, 02071-Albacete, Spain.

Index.

1. Equipment for general procedure2. X-ray crystallographic structure determination3. NMR spectra4. HRMS spectra

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

S2

1. Equipment for general procedure.

Routine NMR spectra were recorded on a Bruker-Avance-400-Ultrashield spectrometer equipped with a BBFO plus SmartProbe. 1H- and 13C{1H}-NMR chemical shifts (δ) are given in ppm relative to TMS. Routine GC-MS analyses were recorded on an Agilent 7890B chromatograph equipped with an Agilent 5977A MSD detector. Additional mass spectra were recorded on a Waters Micromass LCT Premier (ESI). A Bruker-Nonius diffractometer equipped with an Apex II 4K CCD area detector was used for single-crystal diffraction.

2. X-ray crystallographic structure determination.

Table S1. Crystallographic details for Ru1

Crystal data and structure refinement for LB135_25._____________________________________________________________________Identification code LB135_25Empirical formula C52 H62 Cl16 N2 P2 Ru2 Formula weight 1546.31Temperature 100(2) KWavelength 0.71073 ÅCrystal system TriclinicSpace group P-1 Unit cell dimensions a = 10.9333(17)Å α= 69.559(4)°.

b = 11.2468(15)Å β = 77.274(5)°.c = 14.0128(17)Å γ = 84.437(5)°.

Volume 1574.5(4) Å3Z 1Density (calculated) 1.631 Mg/m3

Absorption coefficient 1.246 mm-1F(000) 778Crystal size 0.06 x 0.05 x 0.02 mm3Theta range for data collection 1.583 to 25.164°.Index ranges -12<=h<=13,-12<=k<=13,0<=l<=16Reflections collected 5477Independent reflections 5477[R(int) = 0.0724]Completeness to theta =25.164° 97.2% Absorption correction EmpiricalMax. and min. transmission 0.976 and 0.733Refinement method Full-matrix least-squares on F2Data / restraints / parameters 5477/ 312/ 375Goodness-of-fit on F2 1.144Final R indices [I>2sigma(I)] R1 = 0.0885, wR2 = 0.2374R indices (all data) R1 = 0.1087, wR2 = 0.2490Largest diff. peak and hole 1.950 and -2.003 e.Å-

S3


Crystal data and structure refinement for mo_LB353Cb-055.

_____________________________________________________________________

Identification code mo_LB353Cb-055

Empirical formula C41H78 Cl12 N2P2Ru2

Formula weight 1288.53

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group Cc

Unit cell dimensions a = 18.725(2)Å α= 90°.

b = 13.2472(18)Å β = 93.657(5)°.

c = 22.395(3)Å γ = 90°.

Volume 5543.9(13) Å3

Z 4

Density (calculated) 1.544 Mg/m3

Absorption coefficient 1.212 mm-1

F(000) 2640

Crystal size 0.12 x 0.12 x 0.03 mm3

Theta range for data collection 1.822 to 27.225°.

Index ranges -24<=h<=24,-16<=k<=16,-28<=l<=28

Reflections collected 17328

Independent reflections 17328[R(int) =?]

Completeness to theta =27.225° 96.9%

Absorption correction Multi-scan

Max. and min. transmission 0.965 and 0.742

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 17328/ 644/ 721

Goodness-of-fit on F2 1.075

Final R indices [I>2sigma(I)] R1 = 0.0768, wR2 = 0.2078

R indices (all data) R1 = 0.0814, wR2 = 0.2148

Flack parameter x =-1.2(2)

Largest diff. peak and hole 1.283 and -0.956 e.Å-3

S4


Crystal data and structure refinement for mo_LB337_04.

_____________________________________________________________________

Identification code mo_LB337_04

Empirical formula C50H61Cl7N2P2Ru2





Space group P2(1)/c


b = 36.990(7)Å β = 104.031(5)°.

c = 13.802(2)Å γ = 90°.

Volume 5095.8(15) Å3

Z 4



F(000) 2448






Absorption correction Empirical








S5


Crystal data and structure refinement for mo_LB326_0m._____________________________________________________________________Identification code mo_LB326_0mEmpirical formula C50H60Cl4N2P2Ru2 Formula weight 1094.88Temperature 100(2) KWavelength 0.71073 ÅCrystal system MonoclinicSpace group C2/cUnit cell dimensions a = 19.7175(12)Å α= 90°.

b = 13.6257(8)Å β = 111.7051(15)°.c = 19.4388(12)Å γ = 90°.

Volume 4852.2(5) Å3

Z 4Density (calculated) 1.499 Mg/m3


F(000) 2240Crystal size 0.25 x 0.10 x 0.07 mm3

Theta range for data collection 1.863 to 34.889°.Index ranges -26<=h<=31,-21<=k<=21,-28<=l<=30Reflections collected 50883Independent reflections 10063[R(int) = 0.0232]Completeness to theta =34.889° 94.9% Absorption correction EmpiricalMax. and min. transmission 0.937 and 0.86Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 10063/ 17/ 304Goodness-of-fit on F2 1.059Final R indices [I>2sigma(I)] R1 = 0.0282, wR2 = 0.0677R indices (all data) R1 = 0.0356, wR2 = 0.0734Largest diff. peak and hole 1.534 and -0.625 e.Å-3

S6


Crystal data and structure refinement for LB327b-05.

_____________________________________________________________________

Identification code LB327b-05

Empirical formula C25 H32 Cl2 N P Ru





Space group P2(1)/c


b = 14.1683(7)Å β = 100.4265(14)°.

c = 17.5477(9)Å γ = 90°.

Volume 2458.0(2) Å3

Z 4



F(000) 1128



Index ranges -11<=h<=11,0<=k<=16,0<=l<=21












S7

Table S6. Crystallographic details for Ru11.

Table 1. Crystal data and structure refinement for Ru11.

_____________________________________________________________________

Identification code LB133

Empirical formula C68H58Cl2Fe2N2P4Ru





Space group P2(1)/c

Unit cell dimensions a = 24.374(2) Å α= 90.00 °.

b = 11.4323(10) Å β = 108.050(3) °.

c = 21.033(2) Å γ = 90.00 °.

Volume 5572.5(9) Å3

Z 4



F(000) 2680


Theta range for data collection 0.88 to 29.68 °.

Index ranges -25 <=h<=33 ,-9 <=k<=15 ,-29 <=l<=24


Independent reflections 15625 [R(int) = 0.0771 ]

Completeness to theta =29.68 ° 99.0%




Data / restraints / parameters 15625 / 0 / 712


Final R indices [I>2sigma(I)] R1 = 0.0490 , wR2 = 0.0907

R indices (all data) R1 = 0.0928 , wR2 = 0.1070


S8


Crystal data and structure refinement for Ru13.

_____________________________________________________________________

Identification code LB129_0m

Empirical formula C46H45Cl10FeNP2Ru2




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 10.3629(7)Å α= 82.317(2)°.

b = 13.5134(9)Å β = 84.668(2)°.

c = 18.8728(13)Å γ = 74.300(2)°.

Volume 2517.0(3) Å3

Z 2



F(000) 1284



Index ranges -14<=h<=10,-18<=k<=19,-26<=l<=22


Independent reflections 14486[R(int) = 0.0274]










S9


Crystal data and structure refinement for mo_LB96_0m.

_____________________________________________________________________

Identification code mo_LB96_0m

Empirical formula C75H86B2Cl2F8N2OP4Ru2




Crystal system Orthorhombic

Space group P212121


b = 19.2105(12)Å β = 90°.

c = 36.437(3)Å γ = 90°.

Volume 7221.9(9) Å3

Z 4



F(000) 3288



Index ranges -13<=h<=14,-25<=k<=27,-50<=l<=50


Independent reflections 19482[R(int) = 0.0395]









Flack parameter x =-0.022(5)


S10

3. NMR spectra

Ru1

NN

Ph2P PPh2

Me

Me

Me

iPrRu

Cl Cl

Me

iPrRu

ClCl

1H NMR (500 MHz, CDCl3)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

LB352 2C 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 31

12.0

0

6.05

6.01

2.25

3.97

3.84

3.63

12.0

9

8.04

1.0

21.0

4

1.8

0

2.5

12.5

32.6

12.6

32.6

42.6

63.0

7

4.8

54.8

65.0

0

7.7

47.7

57.7

67.7

67.7

77.7

87.7

8

13C{1H} NMR (101 MHz, CDCl3)

102030405060708090100110120130140150160f1 (ppm)

LB135 ethanol insol 13C.10.fid13C{1H} experiment, 32 scans

17.6

2

22.0

7

30.2

3

38.5

0

50.9

6

87.2

2

89.8

0

96.4

8

111.

49

127.

8012

7.90

130.

1713

2.79

132.

8813

5.80

31P{1H} NMR (202 MHz, CDCl3)

-10-505101520253035404550556065707580859095100105110115120125130f1 (ppm)

LB352 2C 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 31

76.6

4

Figure S1

S11

Ru2NN

Ph2P PPh2

MeMe

Me

iPrRu

Cl Cl

Me

iPrRu

ClCl

1H NMR (400 MHz, CD2Cl2)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

12.5

7

2.94

6.00

8.98

4.88

4.17

4.01

13.4

3

8.60

1.04

1.05

1.53

1.55

1.80

2.51

2.52

2.56

2.58

2.85

2.87

2.87

2.89

2.91

4.91

4.92

4.93

4.93

5.01

5.02

7.35

7.36

7.36

7.37

7.37

7.38

7.39

7.39

7.40

7.40

7.41

7.41

7.41

7.76

7.76

7.78

7.78

7.79

7.80

7.81

13C{1H} NMR (126 MHz, CD2Cl2)

0102030405060708090100110120130140150160170180f1 (ppm)

17.8

122

.31

26.5

830

.76

38.2

338

.25

51.9

651

.97

54.4

3

87.3

787

.42

90.6

2

96.8

0

110.

8311

0.85

128.

0912

8.17

130.

5013

0.52

133.

2313

3.29

31P{1H} NMR (162 MHz, CD2Cl2)

-20-100102030405060708090100110120130140150f1 (ppm)

75.5

7

Figure S2

S12

Ru3NN

(iPr)2P P(iPr)2

MeMe

Me

iPrRu

Cl Cl

Me

iPrRu

ClCl


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

lb358B 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 1

40.5

6

1.99

6.00

6.52

4.45

4.01

3.91

4.05

1.23

1.24

1.26

1.27

1.27

1.28

1.30

1.30

1.31

1.32

1.89

1.89

1.90

1.91

1.92

1.92

1.93

1.94

2.11

2.82

2.84

2.90

2.91

2.92

2.92

2.93

2.93

2.94

2.95

2.95

2.96

2.98

3.11

3.12

3.12

3.13

3.14

3.14

3.15

5.55

5.56

5.63

5.64


05101520253035404550556065707580859095100105110115120125130135140145150f1 (ppm)

lb358B 13C.10.fidResearchGroup ShafirICIQ_13C{1H}512s CDCl3 /opt/topspin lbroomfield 1

18.2

819

.74

19.7

520

.17

22.7

3

29.1

729

.35

30.8

1

38.7

6

51.8

853

.57

85.6

585

.69

87.6

987

.72

95.8

6

108.

58


Figu6668707274767880828486889092949698100102104106108110112114116118120122124126128130132

f1 (ppm)

lb358B 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 1

99.1

6

re S3

S13

Ru4N

NPh2P

PPh2

MeMe

Me

iPrRu

Cl Cl

MeiPr

RuClCl


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

LB352B 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CD2Cl2 /opt/topspin lbroomfield 52

11.5

3

4.00

5.69

1.95

5.80

3.81

4.00

3.35

11.5

0

7.84

1.05

1.07

1.34

1.35

1.36

1.84

2.48

2.49

2.50

2.52

2.53

2.57

2.59

2.98

2.99

4.99

4.99

5.00

5.00

5.06

7.37

7.37

7.38

7.38

7.39

7.40

7.40

7.40

7.41

7.41

7.79

7.79

7.80

7.80

7.81

7.81

7.82

7.82

7.83


0102030405060708090100110120130140150160f1 (ppm)

LB352B 13C.10.fidResearchGroup ShafirICIQ_13C{1H}512s CD2Cl2 /opt/topspin lbroomfield 52 1

7.8

422.3

426.1

926.2

230.7

4

38.0

4

87.4

387.4

890.5

4

97.0

1

110.5

3110.5

5

128.0

3128.1

1130.4

4130.4

6133.2

8133.3

3


-100102030405060708090100110120130140f1 (ppm)

LB352B 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CD2Cl2 /opt/topspin lbroomfield 52

75.3

8

Figure S4

S14

Ru5NH

NH

Ph2P PPh2

Me

iPrRu

Cl Cl

Me

iPrRu

ClCl


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

lb337 1H crude.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 30

3.0

6

6.4

6

3.1

0

2.0

4

1.1

0

1.0

4

2.0

4

2.0

0

6.4

7

4.2

6

0.35

0.82

0.83

1.89

2.07

2.09

2.10

2.55

2.56

2.58

2.59

2.60

2.97

2.98

2.99

2.99

3.00

3.02

4.96

4.97

5.22

5.22

5.23

5.23

7.38

7.39

7.39

7.39

7.39

7.40

7.40

7.41

7.41

7.41

7.42

7.42

7.42

7.43

7.43

7.43

7.43

7.43

7.76

7.76

7.77

7.77

7.77

7.78

7.78

7.78

7.79

7.79

7.80


0102030405060708090100110120130140150160f1 (ppm)

LB-337 13C{1H}.2.fid13C{1H} Experiment

17.5

621

.54

22.8

0

30.2

0

36.8

536

.89

37.2

4

51.1

751

.26

85.9

786

.02

91.3

291

.36

93.5

7

108.

32

128.

0812

8.16

130.

6413

0.66

133.

2713

3.35

133.

9213

4.33

31P{1H} NMR (CDCl3)

-70-60-50-40-30-20-100102030405060708090100110120f1 (ppm)

lb337 31P crude.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 30

63.6

3

Figure S5

S15

Ru6NN

Ph2P PPh2

MeMe

Me

iPrRu

Cl Cl

Me

iPrRu

ClCl


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

lb352 a 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CD2Cl2 /opt/topspin lbroomfield 51

6.00

12.5

3

6.15

2.21

6.13

3.93

4.06

3.87

13.0

2

8.19

0.74

1.05

1.06

1.77

2.46

2.48

2.49

2.49

2.51

2.52

2.59

2.62

2.86

2.87

5.01

5.01

5.02

5.02

5.07

5.08

7.35

7.36

7.36

7.37

7.37

7.37

7.38

7.38

7.38

7.39

7.39

7.39

7.40

7.40

7.40

7.41

7.41

7.41

7.42

7.42

7.42

7.42

7.43

7.43

7.43

7.43

7.44

7.77

7.77

7.78

7.79

7.79

7.79

7.79

7.80

7.80

7.81

7.81


0102030405060708090100110120130140150160170f1 (ppm)

lb352 a 1H.11.fidResearchGroup ShafirICIQ_13C{1H}512s CD2Cl2 /opt/topspin lbroomfield 51 17

.90

22.3

626

.65

30.7

0

39.1

239

.16

39.2

141

.70

41.7

3

64.1

5

87.4

387

.48

90.5

6

97.0

4

110.

6311

0.65

128.

0412

8.12

130.

6813

0.70

133.

8813

3.96


707172737475767778798081828384858687f1 (ppm)

lb352 a 31P.11.fidResearchGroup ShafirICIQ_31P{1H} CD2Cl2 /opt/topspin lbroomfield 51

81.2

6

2DgHSQCped (CDCl3)

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f2 (ppm)

0

20

40

60

80

100

120

f1 (

ppm

)

lb352 a 1H 13C.11.serResearchGroup ShafirICIQ_2DgHSQCped CD2Cl2 /opt/topspin lbroomfield 51

Figure S6

S16

Ru7

NNPPh2

PPh2

Me

iPr Ru

Cl

Cl

Me

iPrRu

Cl

Cl

trans eq.

MeMe


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

lb352C 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CD2Cl2 /opt/topspin lbroomfield 53

2.9

23.2

31.2

51.0

83.1

5

0.9

5

1.0

1

2.6

4

0.8

7

0.8

61.0

20.9

50.9

7

6.1

9

3.9

0

0.9

60.9

71.0

41.0

61.2

11.2

21.2

61.2

71.3

81.3

91.5

91.5

91.8

51.8

8

2.2

32.2

42.2

62.2

72.2

82.2

92.2

92.3

12.7

03.3

35.0

15.0

25.0

55.0

65.1

85.1

95.2

45.2

57.3

27.3

27.3

37.3

37.3

57.3

57.3

57.3

77.3

87.3

87.3

87.3

97.3

97.3

97.4

17.4

17.4

47.4

57.4

67.4

77.4

77.4

77.4

87.4

87.8

47.8

67.9

17.9

37.9

5

13C{1H} NMR (126 MHz, CD2Cl2)

0102030405060708090100110120130140150160f1 (ppm)

lb352C 13C.10.fidResearchGroup ShafirICIQ_13C{1H}512s CD2Cl2 /opt/topspin lbroomfield 53 16

.55

20.9

922

.63

23.8

425

.29

29.9

832

.87

34.6

3

62.8

4

84.5

186

.04

89.8

192

.03

96.2

2

110.

11

126.

1612

6.92

127.

0012

7.75

127.

8212

8.83

129.

8813

0.06

132.

6613

4.84


525354555657585960616263646566676869707172737475767778798081828384f1 (ppm)

lb352C 31P second.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 30

70.9

7

S17

2DgHSQCped (CD2Cl2)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f2 (ppm)

0

50

100

150

f1 (

ppm

)

lb352C 1H 13C.10.serResearchGroup ShafirICIQ_2DgHSQCped CD2Cl2 /opt/topspin lbroomfield 53

VT 1H NMR (500 MHz, CDCl3)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1

2

3

4

5

6

7

LB352C.14.fid1H experiment, 328 K 7







Figure S7

S18

Ru8

HNNHPPh2

PPh2

Me

iPr Ru

Cl

Cl

Me

iPrRu

Cl

Cl

trans ax.


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

LB359B.1.fid1H experiment 298 K

1.21

3.17

3.26

1.04

2.32

3.20

2.11

1.00

1.04

2.10

1.10

2.10

3.24

1.16

4.14

0.5

90.6

70.6

80.8

30.8

41.1

31.3

01.3

2

1.8

2

2.4

42.4

52.4

72.4

8

3.2

83.3

03.3

3

4.8

24.8

35.0

55.0

65.0

75.0

95.2

15.2

27.1

37.1

47.1

57.1

57.1

57.1

67.1

77.2

67.3

57.3

67.3

67.3

87.3

87.3

87.3

97.4

07.4

07.4

17.4

17.4

57.4

67.4

77.4

77.6

27.6

37.6

57.6

97.7

07.7

17.7

2


0102030405060708090100110120130140150160170180190200210f1 (ppm)

LB359B 13C.20.fidResearchGroup ShafirICIQ_13C{1H}512s CDCl3 /opt/topspin lbroomfield 42 17

.38

18.9

520

.95

21.9

426

.14

30.0

9

53.0

0

84.9

886

.91

89.9

291

.98

93.5

9

108.

1012

7.82

127.

9212

8.08

128.

1913

0.24

130.

2713

0.91

130.

9413

2.42

132.

5313

3.37

133.

4713

6.14

136.

68


-70-60-50-40-30-20-100102030405060708090100110120130140150f1 (ppm)

lb359B cyclo 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 120

60.5

3

2DgHSQCped (CDCl3)

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f2 (ppm)

0

50

100

150

f1 (

ppm

)

Figure S8

S19

Ru9

HNPPh2

Me

iPrRu

ClCl


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

lb327 crystals 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 10

6.00

5.95

2.93

0.98

0.96

0.99

1.94

1.89

5.90

3.97

0.72

0.73

0.77

0.78

1.94

2.53

2.55

2.56

2.58

2.59

2.60

2.62

2.70

2.71

2.72

2.72

2.73

2.73

2.74

2.74

2.74

2.75

2.75

2.76

2.76

2.77

2.78

2.79

2.80

2.82

2.83

2.85

5.02

5.03

5.24

5.24

5.25

5.25

7.45

7.45

7.46

7.46

7.47

7.47

7.47

7.47

7.48

7.48

7.48

7.49

7.95

7.95

7.95

7.95

7.96

7.96

7.96

7.96

7.97

7.97

7.97

7.97

7.98

7.98

7.98

7.99


0102030405060708090100110120130140150160170f1 (ppm)

lb327 crystals 13C.11.fidResearchGroup ShafirICIQ_13C{1H}512s CDCl3 /opt/topspin lbroomfield 10 1

7.5

221.3

624.9

925.0

2

30.1

3

45.2

445.3

2

86.2

386.2

891.1

691.2

093.4

8

107.8

7

128.1

0128.1

8130.7

5130.7

7133.1

1133.1

9135.4

4135.8

6


-40-30-20-100102030405060708090100110120130f1 (ppm)

lb327 crystals 31P.11.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 10

60.6

1

Figure S9

S20

Ru10

NPPh2

Me

iPrRu

ClCl


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

lb414 1H cdcl3 2.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 81

1.00

5.81

3.99

0.87

0.89

0.90

1.07

1.08

1.85

2.60

2.61

2.62

2.63

2.64

2.65

2.66

2.68

2.70

3.21

3.23

3.24

3.25

3.25

3.26

3.27

3.29

4.96

4.98

4.98

5.01

7.36

7.37

7.37

7.38

7.38

7.84

7.84

7.85

7.85

7.86

7.86

7.87

7.87

7.87

7.88

7.88

7.89


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

lb414 13C cdcl3 2.10.fidResearchGroup ShafirICIQ_13C{1H}512s CDCl3 /opt/topspin lbroomfield 81 12

.65

12.6

817

.37

22.1

2

30.2

6

41.8

341

.87

86.4

786

.54

90.3

695

.86

111.

10

127.

6412

7.74

129.

9813

0.00

132.

80

31P{1H} NMR (CDCl3)

-505101520253035404550556065707580859095100105110115120125130135140145f1 (ppm)

lb414 31P cdcl3.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 80

75.3

3

Figure S10

S21

Ru11

RuPPh2

N

Ph2P

Ph2PNPPh2

Cl

CliPr iPr


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

LB147B DCM crystals 1H.10.fid1H experiment, 12 ppm, 16 scans

5.9

1

1.0

0

8.0

9

4.1

2

7.6

3

1.0

31.0

5

3.8

23.8

33.8

53.8

73.8

93.9

13.9

2

7.1

07.1

27.1

47.2

87.2

97.2

97.3

07.3

27.6

37.6

47.6

47.6

57.6

67.6

6


0102030405060708090100110120130140150160170180f1 (ppm)

LB147B DCM crystals 13C.10.fid13C{1H} experiment, 32 scans

24.6

4

56.2

3

126.

7612

6.79

126.

8112

9.56

135.

0413

5.07

135.

1113

5.30

135.

41


404244464850525456586062646668707274767880828486889092949698100102104f1 (ppm)

LB147B DCM crystals 31P.10.fid31P{1H} experiment, 16 scans 78

.96

Figure S11

S22

Ru12

RuPPh2

N

Ph2P

Ph2PNPPh2

Cl

ClFe

Fe


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

LB132 etoh insol 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 41

10.0

0

7.63

17.2

0

9.50

16.9

3

3.54

3.78

7.11

7.13

7.14

7.30

7.30

7.30

7.31

7.32

7.33

7.59

7.60

7.60

7.61

7.61

7.62


102030405060708090100110120130140150160170f1 (ppm)

lb132 etoh insol 13C.10.fid13C{1H} experiment, 32 scans

63.7

264

.96

69.6

7

126.

8512

6.88

129.

7313

2.61

134.

6313

4.67

134.

70


-100102030405060708090100110120130140150f1 (ppm)

LB132 etoh insol 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 41

86.9

5

Figure S12

S23

Ru13

PPh2

RuPh2P ClN

Me

iPr

RuCl

Cl

ClFe

1H NMR (400 MHZ, CDCl3)

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

LB129 ethanol insoluble 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 80

5.62

2.80

1.02

5.00

1.94

2.23

2.02

2.11

11.2

4

4.79

4.63

1.1

71.1

9

2.2

0

2.7

12.7

22.7

42.7

63.5

53.6

23.6

33.6

33.7

43.7

53.7

55.1

95.2

15.3

55.3

67.2

87.3

07.3

27.3

47.3

67.3

77.3

87.3

97.4

17.4

37.4

47.6

37.6

47.6

57.6

77.6

77.6

88.0

48.0

58.0

68.0

78.0

9


5101520253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)

LB129-full.3.fid13C{1H} Experiment

18.8

122

.38

24.2

3

31.0

6

62.4

162

.43

62.4

663

.20

69.5

0

78.0

579

.04

95.9

510

0.27

103.

9910

4.09

127.

3212

7.36

127.

4112

7.67

127.

7212

7.76

129.

6513

0.71

132.

2113

2.40

132.

5813

2.73

132.

7713

2.81

134.

2913

4.48

134.

6813

4.94

134.

9813

5.03


4550556065707580859095100105110115120125130135f1 (ppm)

lb129 31P full.10.fid31P{1H} experiment, 16 scans

91.7

6

Figure S13

S24

Ru14

PPh2

Me

iPrRu

Ph2PCl

NiPr

BF4


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

lb351 1H crystals.10.fidResearchGroup ShafirICIQ_1H12p8s CD2Cl2 /opt/topspin lbroomfield 50

12.0

0

12.9

4

6.0

9

2.1

3

2.1

3

4.1

6

4.1

2

40.7

0

0.7

20.7

31.1

11.1

31.9

02.6

82.6

92.7

13.6

53.6

63.6

83.6

93.7

03.7

15.7

75.7

85.9

75.9

97.5

47.5

47.5

47.5

47.5

57.5

57.5

57.5

67.5

67.5

67.5

77.5

77.5

77.5

77.6

17.6

27.6

27.6

27.6

27.6

37.6

57.6

57.6

57.7

07.7

17.7

17.7

27.7

27.7

37.7

37.7

37.7

37.7

37.7

47.7

47.7

47.7

57.7

57.7

57.7

67.7

67.7

67.7

77.7

77.7

87.7

87.7

87.7

97.7

97.7

97.7

9

13C{1H} NMR (101 MHz, CD3OD)

102030405060708090100110120130140150160170f1 (ppm)

LB182 MeOH sol 13C.10.fid13C{1H} experiment, 1024 scans

17.9

822.7

023.9

6

32.8

8

49.6

4

57.2

657.3

157.3

7

92.5

8

96.2

9

109.1

5

127.1

6128.7

4128.8

0128.8

6130.4

3130.4

9130.5

4132.8

0134.1

7134.8

1134.8

7134.9

2134.9

4135.0

0


-50-40-30-20-100102030405060708090100110120130140150f1 (ppm)

lb351 1H crystals.11.fidResearchGroup ShafirICIQ_31P{1H} CD2Cl2 /opt/topspin lbroomfield 50

78.3

9

19F{1H} NMR (376 MHz, CD3OD)

-159.5-159.0-158.5-158.0-157.5-157.0-156.5-156.0-155.5-155.0-154.5-154.0-153.5-153.0-152.5-152.0f1 (ppm)

LB182 MeOH sol 19F.10.fid19F{1H} experiment

3.95

1.00

-154

.83

-154

.78

Figure S14

S25

Ru15

PPh2

Me

iPrRu

Ph2PCl

N

BF4

Fe


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

lb355 Fc 1H.10.fidResearchGroup ShafirICIQ_1H12p8s CDCl3 /opt/topspin lbroomfield 77

6.00

3.04

1.38

4.65

3.09

2.01

1.95

1.90

22.7

7

1.09

1.10

1.83

1.84

1.84

2.58

2.60

2.62

3.41

3.48

3.49

3.49

3.77

3.77

3.78

5.86

5.88

6.03

6.05

7.44

7.45

7.45

7.46

7.47

7.50

7.51

7.51

7.52

7.52

7.62

7.64

7.65

7.66

7.67

7.75

7.77

7.86

7.88

7.90

7.92

7.94

7.95


-100102030405060708090100110120130140150160170180190200f1 (ppm)

lb132B ETOH sol 13C.10.fid13C{1H} experiment, 512 scans

23.0

824

.23

31.9

633

.81

62.6

864

.06

69.6

9

90.8

3

98.0

5

126.

3912

7.73

127.

7912

7.85

129.

0913

0.73

131.

4513

2.69

132.

7413

2.80

133.

6313

5.08

135.

14

126127128129130131132133134135f1 (ppm)

126.

39

127.

7312

7.79

127.

85

129.

09

130.

73

131.

45

132.

6913

2.74

132.

80

133.

63

135.

0813

5.14


-50-40-30-20-100102030405060708090100110120130140f1 (ppm)

lb355 Fc 31P.10.fidResearchGroup ShafirICIQ_31P{1H} CDCl3 /opt/topspin lbroomfield 77

83.6

8

.

Figure S15

S26

Figure S16. 1H-NMR data for the disproportion reaction of Ru7.

NNPPh2

PPh2

Me

iPr Ru

Cl

Cl

Me

iPrRu

Cl

Cl

trans eq.

MeMe

1H NMR

1H NMR

Me

iPrRu(L?)?

No phosphino amine

S27

NNPPh2

PPh2

Me

iPr Ru

Cl

Cl

Me

iPrRu

Cl

Cl

trans eq.

MeMe

MeOHMS analysis

N

N

Me

MePPh2

Ph2PRu Cl

N

N

Me

MePPh2

PPh2

Ru

OMe

Me

iPr

N

N

Me

MePPh2

PPh2

Ru

H

Me

iPr

4. HRMS spectra

N

N

Me

MePPh2

Ph2PRu Cl

N

N

Me

MePPh2

PPh2

Ru

H

Me

iPr

N

N

Me

MePPh2

PPh2

Ru

OMe

Me

iPr

S28

Figure S17. Analysis of a MeCN solution of Ru7 by HRMS.

Documents

Supporting information for Antitumoral Ruthenium(II) Arene ... · Crystal size 0.15 x 0.15 x 0.10 mm3 Theta range for data collection 4.037 to 68.287°. Index ranges -11