Au-iClick mirrors the mechanism of copper catalyzed azide ... · Au-iClick mirrors the mechanism of copper catalyzed azide-alkyne cycloaddition (CuAAC). Andrew R. Powers, Ion Ghiviriga,
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
S1
Supporting Information for
Au-iClick mirrors the mechanism of copper catalyzed azide-alkyne cycloaddition (CuAAC).
Andrew R. Powers, Ion Ghiviriga, Khalil A. Abboud, and Adam S. Veige.*
University of Florida, Department of Chemistry, Center for Catalysis,
Figure S11. 31P{1H} NMR (CDCl3, 121.4 MHz) spectrum of 3-F.
Figure S12. 1H NMR (CDCl3, 300 MHz) spectrum of 3-F.
S10
Figure S13. 19F{1H} NMR (CDCl3, 282.2 MHz) spectrum of 3-F.
Figure S14. 1H-13C gHMBC spectrum (CDCl3, 500 MHz) of 3-F.
S11
General guidelines for kinetic experiments
All kinetic experiments were performed using CDCl3 stock solutions spiked with hexamethyldisiloxane (HMDSO) as an internal standard (0.005 M) against which the product integrations could be referenced. For each set of experiments, a fresh stock solution of azide and acetylide was prepared. To minimize the time a sample was mixed before spectra were collected, a NMR tube charged with a premeasured volume of Au(I)-acetylide stock solution was brought to the NMR instrument and the azide stock solution added to the tube directly prior to loading the sample into the magnet. A lock was already established on the NMR instrument with a similar sample, but to ensure accurate integrations, new lock and shims were established for each sample. Two steady state scans were executed to stabilize the magnetization prior to collection of each spectrum. If a third stock solution needed to be added to the tube (triphenylphosphine), it was mixed with the azide solution directly prior to mixing the azide with the acetylide.
Figure S15. Concentration of 2-H (0.0033 M) as a function of time under varying excess concentrations of 1.
Figure S16. Concentration of 2-NO2 as a function of time when equal concentrations of 1 and 2-NO2 are reacted in the presence of free PPh3.
Figure S17. [2-NO2]-1 as a function of time when equal concentrations of 1 and 2-NO2
are reacted in the presence of free PPh3.
.
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0 5000 10000 15000 20000 25000 30000
[2-N
O2]
(M)
time (s)
0.5 eq PPh3
1.0 eq PPh3
1.5 eq PPh3
2.0 eq PPh3
0
100
200
300
400
500
600
700
800
0 2000 4000 6000 8000 10000 12000
1/[
2-N
O2]
(M-1
)
time (s)
0.5 eq PPh3
1.0 eq PPh3
1.5 eq PPh3
2.0 eq PPh3
S13
Figure S18. Plot of the [2-R] as a function of time under pseudo-first-order conditions of 10-fold excess [1].
Figure S19. Plot of the ln[2-R] as a function of time under pseudo-first-order conditions of 10-fold excess [1].
0
0.0005
0.001
0.0015
0.002
0.0025
0.003
0.0035
0 5000 10000 15000 20000 25000 30000
[2-R
] (M
)
time (s)
R = NO2
R = OMe
R = F
R = H
y = -0.0021x - 5.8968 R² = 0.9987
y = -0.0001x - 5.9155 R² = 0.9836
y = -0.0006x - 5.8289 R² = 0.9807 y = -0.0002x - 5.7151
R² = 0.9981
-10
-9
-8
-7
-6
-5
0 5000 10000 15000 20000 25000
ln[2
-R]
time (s)
R = NO2
R = OMe
R = F
R = H
S14
Figure S20. [2-NO2]-1 as a function of time when equal concentrations of 1 and 2-NO2
are reacted at temperatures ranging from 20-60 °C.
y = 0.0344x + 101.05 R² = 0.9985
y = 0.094x + 81.594 R² = 0.9723
y = 0.2186x + 48.239 R² = 0.991
y = 0.416x + 10.722 R² = 0.9904
y = 1.0535x - 55.535 R² = 0.984
0
100
200
300
400
500
600
700
800
900
1000
0 1000 2000 3000 4000 5000 6000
1/[
2-N
O2]
time (s)
20 C
30 C
40 C
50 C
60 C
S15
Figure S21. Molecular structure of 3-NO2 with ellipsoids presented at 50% probability and hydrogen atoms, and two chloroform lattice molecules are removed for clarity.
X-Ray experimental details for 3-NO2:
X-Ray Intensity data were collected at 100 K on a Bruker SMART diffractometer
using MoK radiation (λ = 0.71073 Å) and an APEXII CCD area detector. Raw data
frames were read by program SAINT1 and integrated using 3D profiling algorithms. The
resulting data were reduced to produce hkl reflections and their intensities and
estimated standard deviations. The data were corrected for Lorentz and polarization
effects and numerical absorption corrections were applied based on indexed and
measured faces.
S16
The structure was solved and refined in SHELXTL6.1, using full-matrix least-
squares refinement. The non-H atoms were refined with anisotropic thermal parameters
and all of the H atoms were calculated in idealized positions and refined riding on their
parent atoms. There are two chloroform solvent molecules in the asymmetric unit, one
of chloroform is partially disordered over two of the chlorine atoms. In this case, atom
C81 should also be disordered but it is to a lesser extent which did not allow for its
resolution. In the final cycle of refinement, 10806 reflections (of which 9294 are
observed with I > 2 (I)) were used to refine 570 parameters and the resulting R1, wR2
and S (goodness of fit) were 2.13%, 4.96% and 0.981, respectively. The refinement
was carried out by minimizing the wR2 function using F2 rather than F values. R1 is
calculated to provide a reference to the conventional R value but its function is not
minimized.
S17
Table S1. Crystal data and structure refinement for 3-NO2.
Identification code apow6 Empirical formula C46H36Au2Cl6N4O2P2 Formula weight 1345.36 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group Pī Unit cell dimensions a = 13.1709(4) Å α= 104.570(2)°.
b = 13.9693(4) Å = 113.005(1)°. c = 15.1962(4) Å γ = 101.240(2)°.
Volume 2352.00(12) Å3 Z 2
Density (calculated) 1.900 Mg/m3
Absorption coefficient 6.682 mm-1 F(000) 1292
Crystal size 0.35 x 0.06 x 0.05 mm3 Theta range for data collection 1.56 to 27.50°. Index ranges -17≤h≤17, -18≤k≤18, -19≤l≤19 Reflections collected 79139 Independent reflections 10806 [R(int) = 0.0712] Completeness to theta = 27.50° 100.0 % Absorption correction Integration Max. and min. transmission 0.7142 and 0.2013
Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10806 / 0 / 570
Goodness-of-fit on F2 0.981 Final R indices [I>2sigma(I)] R1 = 0.0213, wR2 = 0.0496 [9294] R indices (all data) R1 = 0.0274, wR2 = 0.0515
Largest diff. peak and hole 1.577 and -1.305 e.Å-3