Supporting information

Supporting information

Supporting information for the manuscript “MAu2GeS4-chalcogel (M = Co, Ni): heterogeneous intra- and intermolecular hydroamination catalysts” by Bambar Davaasuren,*^† Abdul-Hamid Emwas,^‡ and Alexander Rothenberger*^†

† Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Kingdom of Saudi Arabia

‡ Imaging and Characterization Core Laboratory, King Abdullah University of Science and Technology, 23955–6900 Thuwal, Kingdom of Saudi Arabia

[email protected] and [email protected]

Table S1. Crystallographic data and details on data collection and structure refinement for K2Au2GeS4.

Empirical formula K2Au2GeS4

Formula weight 672.96

Temperature 200(2) K

Radiation Mo Kα

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group C2/c

Unit cell dimensions

a = 7.6435(5) Å b = 14.7750(11) Å c = 8.9921(6) Å β = 114.327(5)°

Volume 925.33(12) ų

ρcalc. 4.831 g/cm³

Absorption coefficient, µ 36.574 mm^-1

F(000) 1168

Crystal size 0.080 x 0.050 x 0.040 mm³

θ range for data collection 2.757 to 29.233°

Reflections collected 4454

Scan type ω-scan

Independent reflections 1189 [Rint = 0.09]

Tmin / Tmax 0.2013 / 0.4311

Refinement method Full-matrix least-squares on F²

Data / parameters 1189 / 43

Goodness-of-fit 1.143

Final R indices [I > 2σ(I)] Robs = 0.0501, wRobs = 0.1309 R indices [all data] Rall = 0.0529, wRall = 0.1348

Solution method / program Direct methods / SHELX2014-WinGX R = Σ||Fo|-|Fc|| / Σ|Fo|, wR = {Σ[w(|Fo|² - |Fc|²)²] / Σ[w(|Fo|⁴)]}^1/2 and

w=1/[σ²(Fo²)+(0.0875P)²+5.7929P] where P=(Fo²+2Fc²)/3

Table S2. Atomic coordinates (x10⁴) and equivalent isotropic displacement parameters (Ųx10³) for K2Au2GeS4 at 200(2) K with estimated standard deviations in parentheses.

Label x y z Occupancy Ueq*

K(1) 0 582(2) 2500 1 29(1)

K(2) 0 3619(2) 2500 1 38(1)

Au(1) 4327(1) 3355(1) 479(1) 1 23(1)

Ge(1) 0 6350(1) 2500 1 20(1)

S(1) 2822(4) 474(2) 640(3) 1 26(1)

S(2) 3523(4) 2173(2) 3691(3) 1 25(1)

*Ueq is defined as one third of the trace of the orthogonalized Uij tensor.

Table S3. Anisotropic displacement parameters (Ųx10³) for K2Au2GeS4 at 200(2) K with estimated standard deviations in parentheses.

Label U11 U22 U33 U12 U13 U23

K(1) 31(2) 28(2) 26(2) 0 10(2) 0

K(2) 35(2) 22(2) 42(2) 0 0(2) 0

Au(1) 22(1) 19(1) 25(1) 1(1) 6(1) 2(1)

Ge(1) 19(1) 16(1) 21(1) 0 6(1) 0

S(1) 23(2) 18(1) 28(1) -1(1) 2(1) -4(1)

S(2) 24(2) 22(1) 28(2) -1(1) 10(1) -4(1)

The anisotropic displacement factor exponent takes the form: -2π²[h²a^*2U11 + ... + 2hka^*b^*U12].

Table S4. Bond lengths [Å] for K₂Au₂GeS₄ at 200(2) K with estimated standard deviations in parentheses.

Label Distances Label Distances

K(1)-S(1)#0 3.169(3) Au(1)-S(2)#0 2.302(2)

K(1)-S(1)#0 3.169(3) Au(1)-S(1)#0 2.312(2)

K(1)-S(1)#0 3.233(3) Au(1)-K(1)#0 3.323(2)

K(1)-S(1) 3.233(3) Au(1)-Au(1)#0 3.345(1)

K(1)-Au(1)#0 3.323(2) Au(1)-K(1)#0 3.692(3)

K(1)-Au(1)#0 3.323(2) Au(1)-K(2)#0 3.971(1)

K(1)-S(2)#0 3.397(3) Au(1)-K(2)#0 4.133(2)

K(1)-S(2) 3.397(3) Ge(1)-S(2)#0 2.213(2)

K(1)-Au(1)#0 3.692(3) Ge(1)-S(2)#0 2.213(2)

K(1)-Au(1)#0 3.692(3) Ge(1)-S(1)#0 2.225(3)

K(1)-Ge(1)#0 3.986(1) Ge(1)-S(1)#0 2.225(3)

K(1)-Ge(1)#0 3.986(1) Ge(1)-K(1)#0 3.986(1)

K(2)-S(2)#0 3.254(3) Ge(1)-K(1)#0 3.986(1)

K(2)-S(2) 3.254(3) S(1)-Ge(1)#0 2.225(3)

K(2)-S(1)#0 3.284(4) S(1)-Au(1)#0 2.312(2)

K(2)-S(1)#0 3.284(4) S(1)-K(1)#0 3.169(3)

K(2)-S(2)#0 3.345(3) S(1)-K(2)#0 3.284(4)

K(2)-S(2)#0 3.345(3) S(2)-Ge(1)#0 2.213(2)

K(2)-Au(1)#0 3.971(1) S(2)-Au(1)#0 2.302(2)

K(2)-Au(1)#0 3.971(1) S(2)-K(2)#0 3.345(3)

K(2)-Au(1)#0 4.133(2) K(2)-Au(1)#0 4.133(2)

K(2)-K(1)#0 4.696(1)

Figure S1. Powder X-ray diffraction pattern of the solid products after removal of water from K2Au2GeS4 aqueous solution.

Figure S2. a) The ¹H NMR spectrum of pure 4-pentyn-1-amine substrate (black line) was measured at room temperature to identify the characteristic resonances. Catalytic activity of Co(OAc)2 was also examined at room temperature (blue line) as well as at 60 °C (red line). The ¹H NMR-results show that Co(OAc)2 was inactive for the hydroamination process at room temperature (blue line), while it started to react with the substrate at 60° C (red line). b) The K2Au2GeS4 does not show any catalytic activity even at 100 °C after 24 h. The ¹H-NMR spectra taken at 0.2h and 24 h are depicted for comparison.

Slight peak shift and broadening is associated with temperature and solvent effect.

Figure S3. H-NMR spectra of the intermolecular hydroamination reaction between aniline and phenylacetylene (top) after 0.2 h and 60 h together with pure substrates spectra, measured at 100 °C.

The HR-MS spectrum clearly confirms (bottom) the formation of (E)-N,1-diphenylethan-1-imine product along with unreacted aniline.

Figure S4. H-NMR spectra of the intermolecular hydroamination reaction between aniline and 1- ethynyl-4-methoxybenzene (top) after 0.2 h and 60 h together with pure substrates spectra, measured at 100 °C. The HR-MS spectrum clearly confirms (bottom) the formation of (E)-1-(4-methoxyphenyl)- N-phenylethan-1-imine product along with unreacted aniline.

Figure S5. H-NMR spectra of the intermolecular hydroamination reaction between aniline and 1- bromo-4-ethynylbenzene (top) after 0.2 h and 60 h together with pure substrates spectra, measured at 100 °C. The HR-MS spectrum clearly confirms (bottom) the formation of (E)-1-(4-bromophenyl)-N- phenylethan-1-imine product along with unreacted aniline.

Figure S6. H-NMR spectra of the intermolecular hydroamination reaction between aniline and 1- fluoro-4-ethynylbenzene (top) after 0.2 h and 60 h together with pure substrates spectra, measured at 100 °C. The HR-MS spectrum clearly confirms (bottom) the formation of (E)-1-(4-fluorophenyl)-N- phenylethan-1-imine product along with unreacted aniline.

F

Figure S7. Observed and calculated powder X-ray diffraction pattern of K2Au2GeS4.

Figure S8. The EDS analysis of the K2Au2GeS4.

Element Wt% At%

GeL 11.06 10.89 AuM 56.39 20.47 SK 22.75 50.73 KK 09.80 17.92 Matrix Correction ZAF

Figure S9. DSC of the K2Au2GeS4 polycrystalline sample showing a strong endothermic effect at 490

°C (Onset point).

Figure S10. The powder XRD pattern of the K2Au2GeS4 before and after DSC cycle. The calculated diffraction pattern for K2Au2GeS4 is given for comparison.

Figure S11. N2-adsorption and desorption isotherms of NiAu2GeS4-chalcogel. The SEM image of the chalcogel is shown in the inset.

Figure S12. a-b) Pore size distribution of MAu2GeS4-aerogel (M = Co, Ni) showing predominantly macroporous nature of the material. c-d) The TG curves of the MAu2GeS4-aerogel (M = Co, Ni) showing the thermal stability of the materials up to 150 °C. e-f) The XRD pattern of the MAu2GeS4- aerogel (M = Co, Ni) before (black) and after (blue) DSC cycle.

Figure S13. The EDS analysis of the MAu2GeS4-aerogel (M = Co, Ni). The K, C, O peaks are associated with the presence of small amount of KOAc, which was not completely removed during washing.

Element Wt% At%

GeL 08.64 09.34

SK 22.52 55.06

CoK 08.80 11.70

AuL 60.04 23.90

Matrix Correction ZAF

Element Wt% At%

GeL 10.43 10.68

SK 24.44 56.68

NiK 09.06 11.48

AuL 56.06 21.16

Matrix Correction ZAF

Figure S14. In-situ ¹H NMR spectra of the evolution of 2-methylpyrroline from 4-pentyn-1-amine at 80 °C using CoAu2GeS4-chalcogel catalyst.

Figure S15. The linear fit of the kinetic data for hydroamination of 4-penthyn-1-amine substrate using CoAu2GeS4-catalyst. The data clearly reflects the first order reaction kinetics with respect to the substrate concentration.

Figure S16. The recoverability results of the CoAu2GeS4-chalcogel catalyst for hydroamination of 4- pentyn-1-amine substrate measured after 1, 2 and 3 catalytic cycles. Duration of each catalytic cycle was 48 h at 100 °C. The catalyst was washed with TCB solvent 5 times after each catalytic cycle to completely remove the reaction products.