Supporting Information

Palladium(II) Complexes Bearing an Indazole-Derived

N-Heterocyclic Carbene and Phosphine Coligands as

Catalysts for the Sonogashira Coupling and the

Hydroamination of Alkynes

Jan C. Bernhammer, Ning Xi Chong, Binbin Zhou, Ramasamy Jothibasu, and Han Vinh Huynh*

Department of Chemistry, National University of Singapore

3 Science Drive 3, 117543 Singapore

Email: chmhhv@nus.edu.sg

2,3-dihydro-1H-pyrazolo[1,2,a]indazolium bromide (1a).

1H NMR (300 MHz, CDCl3)

13C{1H} NMR (75 MHz, CDCl3)

di-µ-bromido-bis(indy-5)dibromidodipalladium(II) (2a).

1H NMR (500 MHz, CD3CN)

13C{1H} NMR (75 MHz, CD3CN)

Thermal ellipsoids at 50% probability, hydrogen atoms omitted for clarity

di-µ-bromido-bis(indy-6)dibromidodipalladium(II) (2b).

1H NMR (500 MHz, CD3CN)

13C{1H} NMR (125 MHz, CD3CN)

Thermal ellipsoids at 50% probability, hydrogen atoms and solvent molecules omitted for clarity

trans-Dibromido(indy-5)(pyridine)palldadium(II) (3a).

1H NMR (300 MHz, CDCl3)

13C{1H} NMR (75 MHz, CDCl3)

Thermal ellipsoids at 50% probability, hydrogen atoms and solvent molecules omitted for clarity

trans-Dibromido(indy-6)(pyridine)palldadium(II) (3b).

1H NMR (300 MHz, CDCl3)

13C{1H} NMR (75 MHz, CDCl3)

Thermal ellipsoids at 50% probability, hydrogen atoms and solvent molecules omitted for clarity

trans-Dibromido(indy-5)(triphenylphosphine)palldadium(II) (4a).

Thermal ellipsoids at 50% probability, hydrogen atoms omitted for clarity

cis-Ditrifluoroacetato(indy-5)(triphenylphosphine)palladium(II) (5a).

1H NMR (300 MHz, CD2Cl2)

13C{1H} NMR (75 MHz, CD2Cl2)

19F {1H} NMR (282 MHz, CD2Cl2)

31P {1H} NMR (122 MHz, CD2Cl2)

Thermal ellipsoids at 50% probability, hydrogen and disordered atoms omitted for clarity

cis-Ditrifluoroacetato(indy-6)(triphenylphosphine)palladium(II) (5b).

1H NMR (300 MHz, CD2Cl2)

13C{1H} NMR (75 MHz, CD2Cl2)

19F {1H} NMR (282 MHz, CD2Cl2)

31P {1H} NMR (122 MHz, CD2Cl2)

Thermal ellipsoids at 50% probability, hydrogen and disordered atoms omitted for clarity

trans-Bromido(indy-5)bis(triphenylphosphine)palladium(II) tetrafluoroborate (6a).

1H NMR (500 MHz, CD3CN)

13C{1H} NMR (125 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

trans-Bromido(indy-6)bis(triphenylphosphine)palladium(II) tetrafluoroborate (6b).

1H NMR (300 MHz, CD3CN)

13C{1H} NMR (75 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

cis-Bromido(indy-5)(dppe)palladium(II) tetrafluoroborate (7a).

1H NMR (500 MHz, CD3CN)

13C{1H} NMR (125 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

cis-Bromido(indy-6)(dppe)palladium(II) tetrafluoroborate (7b).

1H NMR (300 MHz, CD3CN)

13C{1H} NMR (125 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

Thermal ellipsoids at 50% probability, hydrogen and disordered atoms, counteranion and solvent

molecules omitted for clarity

cis-Bromido(indy-5)(dppp)palladium(II) tetrafluoroborate (8a).

1H NMR (500 MHz, CD3CN)

13C{1H} NMR (125 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

Thermal ellipsoids at 50% probability, hydrogen atoms, counteranion and solvent molecules omitted

for clarity

cis-Bromido(indy-6)(dppp)palladium(II) tetrafluoroborate (8b).

1H NMR (300 MHz, CD3CN)

13C{1H} NMR (75 MHz, CD3CN)

19F {1H} NMR (282 MHz, CD3CN)

31P {1H} NMR (122 MHz, CD3CN)

N-(2,6-dimethylphenyl)-1-phenylethylideneamine (11).

Gas chromatogram

Mass spectrum (EI) of product peak at 10.081 min

1-(4-acetylphenyl)-2-phenylethyne (13).

1H NMR (300 MHz, CDCl3)

Selected crystal data, data collection, and refinement parameters for 2a, 2b and 3a

2a 2b·MeCN 3a·MeCN

Formula C12H13Br2N3Pd C15H18Br3N3Pd C17H18Br2Cl0.25N4Pd MW (g/mol) 465.47 520.55 553.44 crystal size (mm) 0.30 × 0.14 × 0.10 0.40 × 0.36 × 0.08 0.24 × 0.12 × 0.10 crystal system Monoclinic Monoclinic Monoclinic space group P2(1)/c P2(1)/c P 21/n a (Å) 9.4099(17) 9.8647(10) 13.4325(6) b (Å) 12.173(3) 11.5490(11) 10.2745(4) c (Å) 12.280(2) 15.5559(16) 13.8594(6) α (°) 90 90 90 β (°) 90.10(2) 94.278(2) 98.377(2) γ (°) 90 90 90 V (Å3) 1406.6(5) 1767.3(3) 1892.36(14) Z 4 4 4 ρcalculated (g/cm3) 2.198 1.956 1.943 temperature (K) 100(2) 100(2) 100(2) Wavelength (Å) 0.71073 0.71073 0.71073 θ (°) 2.36 to 27.46 1.60 to 27.49 2.284 to 27.498 no. of unique reflections 4429 5271 4337 max. and min. transmission 0.5418 and 0.2284 0.6641 and 0.2140 0.7457 and 0.5798 final R indices [I>2σ(I)] R1 = 0.0243,

wR2 = 0.0573 R1 = 0.0310, wR2 = 0.0734

R1 = 0.0291, wR2 = 0.0663

R indices (all data) R1 = 0.0278, wR2 = 0.0573

R1 = 0.0376, wR2 = 0.0752

R1 = 0.0372, wR2 = 0.0693

Goodness-of-fit on F2 1.054 1.015 1.048

Peak/hole (e.Å-3) 0.863 and -0.336 1.007 and -0.650 2.257 and -1.398

Selected crystal data, data collection, and refinement parameters for 3b, 4a and 5a

3b·CHCl3 4a 5a

Formula C17H18Br2Cl3N3Pd C28H25Br2N2PPd C32H25F6N2O4PPd MW (g/mol) 636.91 686.69 752.91

crystal size (mm) 0.236 × 0.091 × 0.054 0.197 × 0.099 × 0.063 0.36 × 0.24 × 0.10 crystal system Orthorhombic Monoclinic Monoclinic space group P b c a P 21/n P 21/n

a (Å) 20.2789(6) 10.6153(8) 10.7241(8) b (Å) 9.4519(3) 16.6679(12) 16.5483(9) c (Å) 21.9379(7) 14.6369(12) 17.6106(12) α (°) 90 90 90 β (°) 90 100.457(3) 96.812(2) γ (°) 90 90 90 V (Å3) 4204.9(2) 2546.8(3) 3103.2(4) Z 8 4 2 ρcalculated (g/cm3) 2.012 1.791 1.612 temperature (K) 100(2) 100(2) 100(2) Wavelength (Å) 0.71073 0.71073 0.71073 θ (°) 2.111 to 27.499 2.302 to 25.370 2.274 to 25.350 no. of unique reflections 4823 4666 5669 max. and min. transmission 0.77 and 0.62 0.7452 and 0.6851 0.7457 and 0.6721 final R indices [I>2σ(I)] R1 = 0.0240,

wR2 = 0.0485 R1 = 0.0369, wR2 = 0.0627

R1 = 0.0446, wR2 = 0.0953

R indices (all data) R1 = 0.0358, wR2 = 0.0513

R1 = 0.0672, wR2 = 0.0701

R1 = 0.0653, wR2 = 0.1018

Goodness-of-fit on F2 1.034 1.011 1.029

Peak/hole (e.Å-3) 0.595 and -0.391 0.835 and -0.579 0.993 and -0.716

Selected crystal data, data collection, and refinement parameters for 5b, 7b and 8a

5b 7b·CH2Cl2 2 8a·3MeCN

Formula C33H27F6N2O4PPd C38H38BBrCl2F4N2P2Pd

C40H40.50Br2N3.50P2Pd MW (g/mol) 766.93 928.66

898.42

crystal size (mm) 0.300 × 0.240 × 0.140 0.300 × 0.280 × 0.100 0.450 × 0.240 × 0.120 crystal system Monoclinic Monoclinic Monoclinic space group P 21/n P 21/c

P 21/n

a (Å) 10.868(10) 17.222(3) 16.9962(10) b (Å) 16.543(15) 17.669(3) 14.4727(10) c (Å) 17.842(16 12.869(2) 30.934(2) α (°) 90 90 90 β (°) 96.674(14) 108.258(3) 96.906(2) γ (°) 90 90 90 V (Å3) 3186(5) 3718.8(10) 7553.9(9) Z 4 4 8 ρcalculated (g/cm3) 1.599 1.659 1.580 temperature (K) 100(2) 100(2) 100(2) Wavelength (Å) 0.71073 0.71073 0.71073 θ (°) 1.684 to 27.499 1.697 to 27.498 2.193 to 28.282 no. of unique reflections 7325 8539 18743 max. and min. transmission 0.5633 and 0.4416 0.8251 and 0.7445 0.7457 and 0.6580 final R indices [I>2σ(I)] R1 = 0.0518,

wR2 = 0.1272 R1 = 0.0351, wR2 = 0.0786

R1 = 0.0558, wR2 = 0.1238

R indices (all data) R1 = 0.0635, wR2 = 0.1338

R1 = 0.0351, wR2 = 0.0786

R1 = 0.0889, wR2 = 0.1369

Goodness-of-fit on F2 1.052 1.048 1.048

Peak/hole (e.Å-3) 1.413 and -1.136 1.032 and -0.652 2.944 and -2.419