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S1

SUPPLEMENTARY INFORMATION

Development of Homogeneous and Heterogenized Rhodium(I) and Palladium(II)

Complexes with Ligands Based on a Chiral Proton Sponge Building Block and their

Application as Catalysts

Gonzalo Villaverde,1,2 Avelina Arnanz,1 Marta Iglesias,1* N. Snejko,1 M. A. Monge,1 and Félix Sánchez2* 1Inst. Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz, 3, Cantoblanco, 28049

Madrid, Spain. 2Inst. Química Orgánica General, CSIC, C/ Juan de la Cierva, 3, 28006 Madrid, Spain.

1H NMR and 13C-NMR:

• Starting chiral amine S3

• Cyclized products (R,R)-5, (R,R)-6 S4-S6

• Imine Compounds (R,R)-7, (R,R)-8 S7-S10

• Pd and Rh complexes S11-S21

UV-Vis and DFTR:

• (R,R)-8 S22

• (R,R)-8Rh S22

• (R,R)-8Rh-MCM S22

• (R,R)-8Pd S22

• (R,R)-8Rh-MCM S22

NMR (before heterogenization), CP-MAS 13C-NMR (after heterogenization):

• 13C-NMR (R,R)-8Pd S23

• 13C-NMR (R,R)-8Pd-MCM S24

• 1H NMR (R,R)-8Pd S25

NMR (before heterogenization), CP-MAS 13C-NMR (after heterogenization):

• 13C-NMR (R,R)-8Rh S26

• 13C-NMR (R,R)-8Rh-MCM S27

• 1H NMR(R,R)-8Rh S28

HPLC Traces S29-S32

Crystallography S33

• Crystallographic and refinement data for (R,R)-6 S34

• Crystallographic and refinement data for (R,R)-7 S35

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011

S2

1H-NMR Starting chiral amine


S3

1H-NMR

(R,R)-5


S4

13C-NMR (R,R)-5


S5

1H-NMR (R,R)-6


S6

13C-NMR (R,R)-6


S7

1H-NMR. (R,R)-7

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

gvco50f1_H1_s2pul_cdcl3_02Std Proton parameters

N

N

OH


S8

13C-NMR (R,R)-7


S9

1H-NMR (R,R)-8


S10

13C-NMR (R,R)-8


S11

1H-NMR (R,R)-5Pd

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

AVI-D-Esponja2+PolCL2CodAVI-D-Eponja2+PolCL2Cod

Pd

N+ N+

N

ClCl


S12

13C-NMR (R,R)-5Pd

0102030405060708090100110120130140150160170180f1 (ppm)

AVI-D-Esponja2+PolCL2CodAVI-D-Eponja2+PolCL2Cod

Pd

N+ N+

N

ClCl


S13

1H-NMR (R,R)-5Rh

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

AVIE-Esponja2+Rhclcod2AVIE-Esponja2+Rhclod2

PF

FF

F

FF

N+N+

NRh


S14

13C-NMR (R,R)-5Rh

0102030405060708090100110120130140150160170f1 (ppm)

AVIE-Esponja2+Rhclcod2AVIE-Esponja2+Rhclod2

PF

FF

F

FF

N+N+

NRh


S15

1H-NMR (R,R)-6Pd

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

N+N

N+

O

Pd

O

O


S16

13C-NMR (R,R)-6Pd

0102030405060708090100110120130140150160170f1 (ppm)

N+N

N+

O

Pd

O

O


S17

CP MAS 13C-NMR (R,R)-6Rh-MCM

N NN

OH

Rh

PF6


S18

1H-NMR (R,R)-7Pd

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

ESP3-PdESP3-Pd

N+ N+

O

Pd

O

O


S19

13C-NMR (R,R)-7Pd

102030405060708090100110120130140150f1 (ppm)

ESP3-PdESP3-Pd

N+ N+

O

Pd

O

O


S20

1H-NMR (R,R)-8Rh

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

ESP3RHESP3RH

PF

FF

F

FF

N+

N+

O Rh

H


S21

13C-NMR (R,R)-8Rh

102030405060708090100110120130140150160170f1 (ppm)

ESP3RHESP3RH

PF

FF

F

FF

N+

N+

O Rh

H


S22

UV-Vis and DFTR

300 400 500 600 700

0,0

0,2

0,4

0,6

0,8

1,0

1,2

A

λ (nm)

88Pd8Pd-MCM-41

300 400 500 600 700

0,0

0,2

0,4

0,6

0,8

1,0

A

λ (nm)

8 8Rh 8Rh-MCM-41


S23

13C-NMR 8Pd-MCM (CP MAS)

N

N

O

NH

ONH

Si

PdO O

O

OO

MC

M-41


S24

13C-NMR (R,R)-8Pd


S25

1H-NMR (R,R)-8Pd


S26

13C-NMR 8Rh-MCM (solid Phase)

N

N

O

NH

ONH

SiO

OO

Rh

MC

M-41


S27

13C-NMR 8Rh


S28

1H-NMR 8Rh


S29

HPLC traces 5Pd 5Rh

Pd/C Pd/C


S30

6Pd 6Rh

Pd/C Pd/C


S31

7Pd 7Rh

Pd/C Pd/C


S32

8Pd-MCM 8Rh-MCM

Pd/C

Pd/C


S33

Single-Crystal X-ray Diffraction.

Data for (R,R)-6 and (R,R-8) were collected on a Bruker Smart CCD diffractometer

equipped with a normal focus, 2.4 kW sealed tube X-ray source (MoKα radiation, λ =

0.71073 Å) operating at 40 kV and 8 mA. Data were collected at room temperature over a

hemisphere of the reciprocal space in a combination of several sets of exposures. Each

exposure of 20s covered 0.5 or 0.3º in ω. Unit cell dimensions were determined by a

least-squares fit of 60 reflections with I >20σ(I). The structures were solved by direct

methods. The final cycles of refinement were carried out by full-matrix least-squares

analyses with anisotropic thermal parameters for all non-hydrogen atoms The final cycles

of refinement were carried out by full-matrix least-squares analyses using SMART

software for data collection and data reduction and SHELXTL1, and anisotropically

refined (Hydrogen atoms were geometrically situated) by full-matrix least-squares

methods on F2 (SHELXL- 97)


S34

Table S1. Crystallographic and refinement data for (R,R)-6.

Identification code (R,R)-6

Empirical formula C28H27N3O

Formula weight 421.53

Temperature 296(2) K

Wavelength 0.71073 Å

Crystal system, space group Orthorhombic, P 21 21 21

Unit cell dimensions

a = 10.414 (3) Å

b = 13.565 (3) Å

c = 15.401(4) Å

Volume 2175.6 (10) Å 3

Z, Calculated density 4, 1.287 Mg/m3

Absorption coefficient 0.079 mm-1

F(000) 896.0

Crystal size 0.4 x 0.3 x 0.2

Theta range for data collection 2.36° to 25.40°

Limiting indices

-12

S35

Table S2. Crystallographic and refinement data for (R,R-7).

Identification code (R,R-7)

Empirical formula C28H34N2O

Formula weight 414.57

Temperature 296(2) K

Wavelength 0.71073 Å

Crystal system, space group Monoclinic, P 21

Unit cell dimensions

a = 9.8047 (8) Å; α = 90°

b = 8.8134 (8) Å; β = 91.363 (1)

c = 14.0070 (12) Å; γ = 90 °

Volume 1210.04 (18) Å 3

Z, Calculated density 2, 1.138 Mg/m3

Absorption coefficient 0.069 mm-1

F(000) 448.0

Crystal size 0.45 x 0.3 x 0.2

Theta range for data collection 2.31° to 25.39°

Limiting indices

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