supplementary information - nature · 2014-01-23 · zheng, j., zhao, y. & truhlar, d. g....

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1843

Supporting Information for

Biosynthetic Consequences of Multiple Sequential Post-‐

Transition State Bifurcations

Young Joo Hong & Dean J. Tantillo

Department of Chemistry, University of California–Davis, One Shields Avenue, Davis, CA 95616,

USA

Biosynthetic consequences of multiple sequential post-‐transition-‐state bifurcations

Biosynthetic consequences of multiple sequential post-‐transition-‐state bifurcations

© 2014 Macmillan Publishers Limited. All rights reserved.



SI-‐2

Table of Contents I. Methods SI-‐4 2. Gaussian References SI-‐7 3. Dynamics Simulation Trajectories SI-‐8

3.1. Movies of representative trajectories SI-‐8 3.1.1. Movie 1: A2-‐TS10re-‐D1/D2 SI-‐8 3.1.2. Movie 2: A2-‐TS10re-‐G1/G2 SI-‐8 3.1.3. Movie 3: B2-‐TS10re-‐F2 SI-‐9 3.1.4. Movie 4: B2-‐TS10re-‐I1 SI-‐9 3.1.5. Movie 5: A2-‐TS10re-‐J1 SI-‐10 3.1.6. Movie 6: B2-‐TS10re-‐L1 SI-‐10 3.1.7. Movie 7: B2-‐TS10re-‐H1/H2 SI-‐11 3.1.8. Movie 8: B2-‐TS10re-‐H3 SI-‐11

3.2. Summary of trajectories initiated near TS2si SI-‐12 3.2.1. Table S1: productive SI-‐12 3.2.2. Table S2: nonproductive (recrossing) SI-‐12 3.3. Summary of trajectories initiated near TS10re SI-‐13 3.3.1. Table S3: productive SI-‐13 3.3.2. Table S4: nonproductive (recrossing) SI-‐13 3.4. Summary of trajectories initiated near TS12 SI-‐14 3.4.1. Table S5 SI-‐14 3.5. Representative trajectories initiated near TS2si SI-‐15

3.5.1. Figure S1: A1, B1 SI-‐15 3.5.2. Figure S2: D1, E1 SI-‐16 3.5.3. Figure S3: G1, G2 SI-‐16 3.5.4. Figure S4: H1, H2 SI-‐17 3.5.5. Figure S5: I1 SI-‐17 3.5.6. Figure S6: L1 SI-‐18 3.5.7. Figure S7: N1 SI-‐19 3.5.8. Figure S8: P1 SI-‐19

3.6. Representative trajectories initiated near TS10re SI-‐20 3.6.1. Figure S9: A2, B2 SI-‐20 3.6.2. Figure S10: D2, D3 SI-‐21 3.6.3. Figure S11: F2 SI-‐21 3.6.4. Figure S12: H1, H2 SI-‐22 3.6.5. Figure S13: I1 SI-‐22 3.6.6. Figure S14: J1 SI-‐23 3.6.7. Figure S15: L1 SI-‐23

3.7. Representative trajectories initiated near TS12 SI-‐24 3.7.1. Figure S16: D2, D3 SI-‐24 3.7.2. Figure S17: F2 SI-‐24 3.7.3. Figure S18: G1, G2 SI-‐25




SI-‐3

3.7.4. Figure S19: H1, H2 SI-‐25 3.7.5. Figure S20: H3 SI-‐26 3.7.6. Figure S21: K1 SI-‐26 3.7.7. Figure S22: L1 SI-‐27 3.7.8. Figure S23: M1 SI-‐27

4. Coordinates and Energies SI-‐28 4.1. Figure 3 (Full system) SI-‐28 4.1.1. Minimum carbocation SI-‐28 4.1.2. Transition state structure SI-‐69

4.2. Figure 4 (Small model system) SI-‐112 4.2.1. Minimum carbocation SI-‐112

4.2.2. Transition state structure SI-‐148 5. IRC Plots SI-‐184 5.1. Representative IRC Plots SI-‐184 5.1.1. Figure S24: TS2si SI-‐184 5.1.2. Figure S25: TS3 SI-‐185 5.1.3. Figure S26: TS4 SI-‐185 5.1.4. Figure S27: TS7 SI-‐186

5.1.5. Figure S28: TS10re SI-‐186 5.1.6. Figure S29: TS11 SI-‐187 5.1.7. Figure S30: TS12 SI-‐187 5.2. IRC plots SI-‐188 5.2.1. Figure 3 (Full system) SI-‐188 5.2.2. Figure 4 (Small model system) SI-‐188




SI-‐4

1. METHODS

All calculations were performed with Gaussian031 and Gaussian092. All geometries were

optimized using B3LYP/6-31+G(d,p)3-7. Computed energies using mPW1PW918 and

MPWB1K9-10 with the same basis set used in geometry optimization are also reported. These

levels of theory have been used in many previous studies on terpene-forming carbocation

rearrangements.11 All stationary points were characterized by frequency calculations and

reported energies include zero-point energy corrections (unscaled) from the method used for

geometry optimization. Intrinsic reaction coordinate (IRC) calculations12-13 were used for further

characterization of all transition state structures. Energies shown in the IRC plots included as

Supplementary Information do not include zero-point energy corrections. Whenever a

bifurcation was suspected, the second transition state structure directly connected to the

transition state structure preceding the bifurcation was sought. Structural drawings in the

Supplementary Information were produced using Ball & Stick14.

All dynamics calculations were performed using Progdyn15. Truncated model systems (See

Figure 4) were used due to the computational cost associated with running hundreds of dynamics

trajectories. The PES for the model systems is very similar to that for the full-sized system; see

Supplementary Information for details. Trajectory calculations made use of B3LYP/6-31+G(d,p)

and were quasiclassical in nature, i.e., included zero-point energies (298.15°K). Trajectories

were initiated in both the reactant and product directions from the region of a particular transition

state structure. Trajectories were terminated using the following criteria: C9–H



SI-‐5

unproductive, and trajectories terminating near structure C (19%) also were deemed

unproductive for the sake of arguments discussed in the main text.

1. Frisch, M. J. et al. Gaussian03, revision D.01 (Gaussian, Pittsburgh, Pennsylvania, 2003).

2. Frisch, M. J. et al. Gaussian09, revision A.02 (Gaussian, Pittsburgh, Pennsylvania, 2009).

3. Becke, A. D. Density-functional Thermochemistry. 3. The Role of Exact Exchange. J. Chem.

Phys. 98, 5648–5652 (1993).

4. Becke, A. D. A New Mixing of Hartree–Fock and Local Density–function Theories. J. Chem.

Phys. 98, 1372–1377 (1993).

5. Lee, C., Yang, W. & Parr, R. G. Development of the Colle–Salvetti Correlation-energy

Formula into a Functional of the Electron Density. Phys. Rev. B 6, 785–789 (1988).

7. Stephens, P. J., Devlin, F. J., Chabalowski, C. F. & Frisch, M. J. Ab initio Calculation of

Vibrational Absorption and Circular-dichroism Spectra using Density-functional Force-fields. J.

Phys. Chem. 98, 11623–11627 (1994).

8. Matsuda, S. P. T., Wilson, W. K. & Xiong, Q. Mechanistic Insights into Triterpene Synthesis

from Quantum Mechanical Calculations. Detection of Systematic Errors in B3LYP Cyclization

Energies. Org. Biomol. Chem. 4, 530–543 (2006).

9. Zhao, Y. & Truhlar, D. G. Hybrid Meta Density Functional Theory Methods for

Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions: The MPW1B95 and

MPWB1K Models and Comparative Assessments for Hydrogen Bonding and van der Waals

Interactions. J. Phys. Chem. A 108, 6908–6918 (2004).

10. Zheng, J., Zhao, Y. & Truhlar, D. G. Representative Benchmark Suites for Barrier Heights of

Diverse Reaction Types and Assessment of Electronic Structure Methods for Thermochemical

Kinetics. J. Chem. Theory Comput. 3, 569–582 (2007).

11. Tantillo, D. J. Biosynthesis via Carbocations: Theoretical Studies on Terpene Formation.

Nat. Prod. Rep. 28, 1035-1053 (2011).

12. Fukui, K. The path of Chemical Reactions – The IRC Approach. Acc. Chem. Res. 14, 363–

368 (1981).

13. Gonzalez, C. & Schlegel, H. B. Reaction Path Following in Mass-weighted Internal

Coordinates. J. Phys. Chem. 94, 5523–5527 (1990).

14. Müller, N., Falk, A. & Gsaller, G. Ball & Stick V.4.0a12, Molecular Graphics Application for




SI-‐6

MacOS Computers (Johannes Kepler University, Linz, 2004).

15. Kelly, K. K., Hirschi, J. S. & Singleton, D. A. Newtonian Kinetic Isotope Effects.

Observation, Prediction, and Origin of Heavy-atom Dynamic Isotope Effects. J. Am. Chem. Soc.

131, 8382-8383 (2009).

16. Wang, Z., Hirschi, J. S. & Singleton, D. A. Recrossing and Dynamic Matching Effects on

Selectivity in a Diels-Alder Reaction. Angew. Chem. Int. Ed. 48, 9156-9159 (2009).




SI-‐7

2. Gaussian References

Gaussian 03 Full Reference: GAUSSIAN03, Revision D.01 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-‐Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.

Gaussian 09 Full reference: Gaussian 09, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2010.




SI-‐8

3. Dynamics Simulation Trajectories 3.1. Movies of representative trajectories The trajectories initiated near TS10re are shown. 3.1.1. Movie 1: A2-‐TS10re-‐D2/D3 3.1.2. Movie 2: A2-‐TS10re-‐G1/G2




SI-‐9

3.1.3. Movie 3: B2-‐TS10re-‐F2

3.1.4. Movie 4: B2-‐TS10re-‐I1




SI-‐10

3.1.5. Movie 5: A2-‐TS10re-‐J1

3.1.6. Movie 6: B2-‐TS10re-‐L1




SI-‐11

3.1.7. Movie 7: B2-‐TS10re-‐H1/H2 3.1.8. Movie 8: B2-‐TS10re-‐H3




SI-‐12

3.2. Summary of trajectories initiated near TS2si 3.2.1. Table S1: productive Table S1. Summary of productive trajectories initiated near TS2si.

A1

G1, G2

B1

D1, E1

N1

H1, H2

I1

L1

4 0

0 1

2 0

81 19

7 5

1

25 4

4 2

0

4

1

2

100

12

1

29

6

155Total

reactantproductive trajectory

124 31

P1

C

3.2.2. Table S2: nonproductive (recrossing) Table S2. Summary of nonproductive trajectories initiated near TS2si.

A1

B1

3 0

17

A1

H1, H2

B1 H1, H2

4

Total 15 11

recrossing trajectory

4




SI-‐13

3.3. Summary of trajectories initiated near TS10re 3.3.1. Table S3: productive Table S3. Summary of productive trajectories initiated near TS10re.

A2

G1, G2

B2

D2, D3

F2

H1, H2

H3

G3

I1

J1

L1

26 58

48 45

1 2

2 3

1 2

1

1 1

2 1

10

0

84

93

3

5

3

1

2

3

1

195Total

reactantproductive trajectory

82 113

3.3.2. Table S4: nonproductive (recrossing) Table S1. Summary of nonproductive trajectories initiated near TS10re.

A2

B2

5 0

60

A2

G1, G2

B2 D2, D3 G1, G2

21

Total 14 11

recrossing trajectory

3




SI-‐14

3.4. Summary of trajectories initiated near TS12 3.4.1. Table S5 Table S5. Summary of trajectories initiated near TS12.

G1, G2

D2, D3

F2

H1, H2

H3

M1

L1

44

7

110

56

2

2

8

1

1

187Total 231

trajectory productive nonproductive

44

K1

C




SI-‐15

3.5. Representative trajectories initiated near TS2si 3.5.1. Figure S1: A1, B1

Figure S1. Representative trajectories initiated near TS2si to lead to A1 (TOP) and B1 (BOTTOM).




SI-‐16

3.5.2. Figure S2: D1, E1

Figure S2. Representative trajectory initiated near TS2si to lead to D1 and E1. 3.5.3. Figure S3: G1, G2

Figure S3. Representative trajectories initiated near TS2si to lead to G1 and G2.




SI-‐17

3.5.4. Figure S4: H1, H2

Figure S4. Representative trajectories initiated near TS2si to lead to H1 and H2. 3.5.5. Figure S5: I1

Figure S5. Representative trajectories initiated near TS2si to lead to I1.




SI-‐18

3.5.6. Figure S6: L1

Figure S6. Representative trajectories initiated near TS2si to lead to L1 (BOTTOM: close-‐up).




SI-‐19

3.5.7. Figure S7: N1

Figure S7. Representative trajectories initiated near TS2si to lead to N1. 3.5.8. Figure S8: P1

Figure S8. Representative trajectories initiated near TS2si to lead to P1.




SI-‐20

3.6. Representative trajectories initiated near TS10re 3.6.1. Figure S9: A2, B2

Figure S9. Representative trajectories initiated near TS10re to lead to A2 (LEFT), B2 (RIGHT).




SI-‐21

3.6.2. Figure S10: D2, D3

Figure S10. Representative trajectories initiated near TS10re to lead to D2 and D3. 3.6.3. Figure S11: F2

Figure S11. Representative trajectories initiated near TS10re to lead to F2.




SI-‐22

3.6.4. Figure S12: H1, H2

Figure S12. Representative trajectories initiated near TS10re to lead to H1 and H2.

3.6.5. Figure S13: I1

Figure S13. Representative trajectories initiated near TS10re to lead to I1.




SI-‐23

3.6.6. Figure S14: J1

Figure S14. Representative trajectory initiated near TS10re to lead to J1.

3.6.7. Figure S15: L1

Figure S15. Representative trajectories initiated near TS10re to lead to L1.




SI-‐24

3.7. Representative trajectories initiated near TS12 3.7.1. Figure S16: D2, D3

Figure S16. Representative trajectories initiated near TS12 to lead to D2 and D3.

3.7.2. Figure S17: F2

Figure S17. Representative trajectories initiated near TS12 to lead to F2.




SI-‐25

3.7.3. Figure S18: G1, G2

Figure S18. Representative trajectories initiated near TS12 to lead to G1 and G2.

3.7.4. Figure S19: H1, H2

Figure S19. Representative trajectories initiated near TS12 to lead to H1 and H2.




SI-‐26

3.7.5. Figure S20: H3

Figure S20. Representative trajectories initiated near TS12 to lead to H3.

3.7.6. Figure S21: K1

Figure S21. Representative trajectories initiated near TS12 to lead to K1.




SI-‐27

3.7.7. Figure S22: L1

Figure S22. Representative trajectory initiated near TS12 to lead to L1.

3.7.8. Figure S23: M1

Figure S23. Representative trajectory initiated near TS12 to lead to M1.




SI-‐28

4. Coordinates and Energies 4.1. Figure 3 (Full system) 4.1.1. Minimum Carbocation A1 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7856466 hartrees (-‐490578.311097966 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.486782 (Hartree/Particle)

93o1.65

1.44

1.46

1.541.491.36

1.5413

9

8

1516

17142.45

1.11

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 3.120100 -‐1.075716 -‐0.802642 2 6 3.517122 0.173582 0.006629 3 6 2.574209 1.323041 -‐0.451665 4 6 0.651204 -‐0.322516 -‐0.269149 5 6 1.614453 -‐1.437316 -‐0.754041 6 1 3.411006 -‐0.890744 -‐1.842831 7 1 1.453265 -‐2.300586 -‐0.106375 8 1 1.295399 -‐1.749238 -‐1.751081 9 1 3.716517 -‐1.932897 -‐0.477258 10 1 0.781057 -‐0.316785 0.859097 11 6 4.969903 0.583118 -‐0.326073 12 1 5.658396 -‐0.220854 -‐0.052137 13 1 5.086324 0.785301 -‐1.396831 14 1 5.269767 1.480296 0.225370 15 6 3.401493 0.016672 1.514444 16 6 3.175800 -‐1.107539 2.202524 17 6 1.128736 1.046831 -‐0.335130 18 1 2.821022 2.290655 0.002174 19 6 0.225953 2.196666 -‐0.107868 20 1 0.459242 2.487008 0.936150 21 1 0.596855 3.053824 -‐0.688472




SI-‐29

22 1 3.576879 0.936520 2.075846 23 1 3.166885 -‐1.102254 3.288070 24 1 2.719195 1.467218 -‐1.541118 25 6 -‐1.278404 1.953262 -‐0.265497 26 1 -‐1.804605 2.736959 0.283607 27 1 -‐1.558375 2.076156 -‐1.315391 28 6 -‐1.672706 0.560176 0.252733 29 6 -‐0.886286 -‐0.551704 -‐0.531729 30 6 -‐1.280341 -‐1.943915 0.023344 31 1 -‐0.804980 -‐2.732778 -‐0.569332 32 1 -‐0.893311 -‐2.043063 1.048868 33 6 -‐2.797197 -‐2.162421 0.058411 34 6 -‐3.224620 0.361395 0.423145 35 6 -‐3.485913 -‐1.088504 0.904185 36 1 -‐3.205535 -‐2.177946 -‐0.959167 37 1 -‐3.004457 -‐3.152927 0.477889 38 1 -‐4.567903 -‐1.262645 0.931739 39 1 -‐3.134322 -‐1.183871 1.941913 40 1 -‐1.293725 0.490801 1.286908 41 6 -‐1.106479 -‐0.508106 -‐2.063837 42 1 -‐0.763578 0.429940 -‐2.513490 43 1 -‐0.573429 -‐1.322690 -‐2.561024 44 1 -‐2.158329 -‐0.621566 -‐2.320184 45 6 -‐4.058376 0.661348 -‐0.843633 46 1 -‐3.834909 1.648185 -‐1.261720 47 1 -‐3.929417 -‐0.077163 -‐1.637444 48 1 -‐5.121351 0.660084 -‐0.581538 49 6 -‐3.721923 1.315098 1.535813 50 1 -‐4.758830 1.075424 1.792190 51 1 -‐3.126780 1.215308 2.451143 52 1 -‐3.706887 2.365809 1.229025 53 1 3.028564 -‐2.072205 1.725634 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6207628 hartrees (-‐490474.844864628 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.346078 hartrees (-‐490302.47740578 kcal/mol) A2 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7907332 hartrees (-‐490581.502990332 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.489086 (Hartree/Particle)




SI-‐30

1.341.45

1.70

1.481.47

1312

98

15

16

17

14

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 -‐2.702402 -‐1.565910 0.171126 2 6 -‐3.377532 -‐0.198196 0.427222 3 6 -‐2.262140 0.806652 0.819920 4 6 -‐0.618110 -‐0.325244 -‐0.782788 5 6 -‐1.611913 -‐1.501787 -‐0.907842 6 1 -‐2.297863 -‐1.935968 1.120507 7 1 -‐2.094651 -‐1.393802 -‐1.885601 8 1 -‐1.072377 -‐2.449793 -‐0.945504 9 1 -‐3.461204 -‐2.293132 -‐0.138327 10 1 -‐0.255689 -‐0.040455 -‐1.775750 11 6 -‐4.390553 -‐0.315432 1.585358 12 1 -‐5.201551 -‐0.999086 1.316303 13 1 -‐3.911547 -‐0.704764 2.490545 14 1 -‐4.838403 0.655209 1.819748 15 6 -‐4.104421 0.258315 -‐0.823939 16 6 -‐3.921593 1.382953 -‐1.523673 17 6 -‐1.120422 0.865017 -‐0.117696 18 1 -‐2.652035 1.809463 1.019523 19 6 -‐0.339748 2.108841 -‐0.251471 20 1 -‐0.187232 2.342515 -‐1.311968 21 1 -‐0.826520 2.957104 0.234335 22 1 -‐1.830942 0.458643 1.777140 23 6 1.083652 1.855648 0.373941 24 1 1.663114 2.759115 0.175012 25 1 0.989272 1.772850 1.460844 26 6 1.734744 0.617753 -‐0.244509 27 6 0.864966 -‐0.661895 -‐0.031348 28 6 1.484101 -‐1.838744 -‐0.818274 29 1 0.930419 -‐2.763307 -‐0.630769 30 1 1.416416 -‐1.634565 -‐1.894817




SI-‐31

31 6 2.964110 -‐2.050570 -‐0.447123 32 6 3.272419 0.464712 0.088840 33 6 3.792251 -‐0.783750 -‐0.668452 34 1 3.053929 -‐2.397604 0.588292 35 1 3.356655 -‐2.863606 -‐1.067957 36 1 4.834407 -‐0.962650 -‐0.378556 37 1 3.808279 -‐0.557544 -‐1.744007 38 1 1.732705 0.778888 -‐1.333230 39 6 0.617796 -‐1.072923 1.427648 40 1 -‐0.177132 -‐1.820674 1.486692 41 1 1.507436 -‐1.535726 1.853774 42 1 0.351784 -‐0.237869 2.081024 43 6 3.600482 0.371368 1.594990 44 1 3.176299 1.207636 2.160462 45 1 3.262896 -‐0.555404 2.062132 46 1 4.686129 0.416552 1.728375 47 6 4.023924 1.694768 -‐0.473277 48 1 5.102715 1.512046 -‐0.440655 49 1 3.757266 1.893502 -‐1.517698 50 1 3.838363 2.602488 0.109184 51 1 -‐4.510990 1.590455 -‐2.411146 52 1 -‐3.212086 2.156526 -‐1.240258 53 1 -‐4.875534 -‐0.436494 -‐1.159581 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6244884 hartrees (-‐490477.182715884 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.3496917 hartrees (-‐490304.745038667 kcal/mol) B1 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7897444 hartrees (-‐490580.882508444 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.487750 (Hartree/Particle)

1.12

3.441.47

1.34

1.52

1.491.48

139

8

15

16

17

Coordinates (from last standard orientation):




SI-‐32

-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 -‐2.988898 1.059799 -‐0.808272 2 6 -‐3.518825 -‐0.171311 -‐0.051055 3 6 -‐2.551150 -‐1.336348 -‐0.349849 4 6 -‐0.567992 0.279137 -‐0.369708 5 6 -‐1.526753 1.395772 -‐0.470056 6 1 -‐3.069692 0.873459 -‐1.885693 7 1 -‐1.480718 1.799811 0.564982 8 1 -‐1.130726 2.206232 -‐1.087051 9 1 -‐3.602439 1.943428 -‐0.608549 10 1 -‐1.057843 -‐0.873525 1.126556 11 6 -‐4.927662 -‐0.539386 -‐0.573585 12 1 -‐5.626199 0.286464 -‐0.411937 13 1 -‐4.900063 -‐0.765303 -‐1.645502 14 1 -‐5.322434 -‐1.417438 -‐0.052724 15 6 -‐3.608071 0.034846 1.454533 16 6 -‐3.622799 1.191054 2.126566 17 6 -‐1.077986 -‐1.047063 0.019333 18 1 -‐2.861486 -‐2.237452 0.190020 19 6 -‐0.150657 -‐2.236238 -‐0.288319 20 1 -‐0.513890 -‐3.093297 0.285312 21 1 -‐0.307384 -‐2.499362 -‐1.340397 22 1 -‐3.726439 -‐0.889305 2.023714 23 1 -‐3.736439 1.208331 3.206011 24 1 -‐2.597783 -‐1.584432 -‐1.417764 25 6 1.349945 -‐1.988543 -‐0.010361 26 1 1.676561 -‐2.627866 0.812011 27 1 1.925551 -‐2.305263 -‐0.883451 28 6 1.696623 -‐0.529010 0.347314 29 6 0.894270 0.504866 -‐0.531160 30 6 1.313259 1.969361 -‐0.211892 31 1 0.871450 2.661099 -‐0.935755 32 1 0.913096 2.240094 0.774450 33 6 2.832342 2.167808 -‐0.182678 34 6 3.247862 -‐0.280866 0.483796 35 6 3.490362 1.211563 0.810791 36 1 3.258230 2.043538 -‐1.185070 37 1 3.036117 3.206164 0.100503 38 1 4.569912 1.394659 0.854373 39 1 3.102045 1.424418 1.817340




SI-‐33

40 1 1.315713 -‐0.347371 1.364661 41 6 1.021252 0.259654 -‐2.095017 42 1 0.812473 -‐0.769154 -‐2.389746 43 1 0.367905 0.930479 -‐2.659561 44 1 2.049911 0.489022 -‐2.374080 45 6 4.077974 -‐0.687674 -‐0.755994 46 1 3.956949 -‐1.744810 -‐1.008067 47 1 3.851963 -‐0.102856 -‐1.650618 48 1 5.140031 -‐0.534598 -‐0.538843 49 6 3.767950 -‐1.111903 1.680567 50 1 4.807793 -‐0.842943 1.892671 51 1 3.187129 -‐0.919036 2.590093 52 1 3.748831 -‐2.187703 1.483410 53 1 -‐3.564397 2.161408 1.638973 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6244255 hartrees (-‐490477.143245505 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.3495423 hartrees (-‐490304.651288673 kcal/mol) B2 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7899232 hartrees (-‐490580.994707232 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.487809 (Hartree/Particle)

1.47

1.491.48

1.12

3.37 1.34

9

8

15

16

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 -‐2.936312 1.443983 -‐0.464993 2 6 -‐3.537650 0.078767 -‐0.065800 3 6 -‐2.620478 -‐1.006718 -‐0.657682 4 6 -‐0.567040 0.479704 -‐0.237197




SI-‐34

5 6 -‐1.487617 1.607617 0.021799 6 1 -‐2.967619 1.552685 -‐1.555893 7 1 -‐1.487923 1.647969 1.132532 8 1 -‐1.048243 2.560068 -‐0.282838 9 1 -‐3.532196 2.265221 -‐0.053130 10 1 -‐1.057185 -‐1.057230 0.822549 11 6 -‐4.954157 -‐0.052798 -‐0.673072 12 1 -‐5.626561 0.708028 -‐0.264431 13 1 -‐4.925632 0.070405 -‐1.761444 14 1 -‐5.382344 -‐1.033376 -‐0.446536 15 6 -‐3.660331 0.007770 1.449776 16 6 -‐3.346457 -‐1.015023 2.252484 17 6 -‐1.125934 -‐0.878378 -‐0.283246 18 1 -‐2.957904 -‐2.006353 -‐0.366675 19 6 -‐0.253227 -‐1.937667 -‐0.982436 20 1 -‐0.645507 -‐2.920432 -‐0.706654 21 1 -‐0.435049 -‐1.839613 -‐2.058464 22 1 -‐2.697528 -‐0.971739 -‐1.751400 23 6 1.259743 -‐1.846707 -‐0.677687 24 1 1.572606 -‐2.736586 -‐0.128027 25 1 1.810908 -‐1.867340 -‐1.621147 26 6 1.666178 -‐0.604999 0.142082 27 6 0.903844 0.690843 -‐0.326174 28 6 1.374387 1.944445 0.468465 29 1 0.958854 2.855958 0.028191 30 1 0.982663 1.876144 1.492278 31 6 2.899813 2.068447 0.545723 32 6 3.225738 -‐0.473385 0.330685 33 6 3.524034 0.808554 1.144012 34 1 3.321002 2.279691 -‐0.444039 35 1 3.141047 2.940024 1.163844 36 1 4.609715 0.929331 1.230802 37 1 3.146857 0.678383 2.168596 38 1 1.294772 -‐0.761548 1.167425 39 6 1.027161 0.985838 -‐1.881092 40 1 0.385467 1.817295 -‐2.184964 41 1 2.059117 1.281613 -‐2.071019 42 1 0.801780 0.118842 -‐2.502837 43 6 4.036112 -‐0.458905 -‐0.986475 44 1 3.865540 -‐1.356015 -‐1.588036 45 1 3.836630 0.409965 -‐1.617609 46 1 5.104451 -‐0.437100 -‐0.748187 47 6 3.717739 -‐1.680557 1.163439




SI-‐35

48 1 4.764618 -‐1.531503 1.446792 49 1 3.140405 -‐1.795874 2.088137 50 1 3.666796 -‐2.621194 0.607454 51 1 -‐3.519391 -‐0.959045 3.322702 52 1 -‐2.947617 -‐1.957528 1.884195 53 1 -‐4.105814 0.895859 1.902177 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6246955 hartrees (-‐490477.312673205 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.3499875 hartrees (-‐490304.930656125 kcal/mol) C B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7783751 hartrees (-‐490573.748159001 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.487470 (Hartree/Particle)

93o1.65

1.44

1.46

1.541.491.36

1.5413

9

8

1516

17142.45

1.11

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 -‐3.036031 1.308544 -‐0.594771 2 6 -‐3.646537 0.015434 -‐0.016409 3 6 -‐2.601820 -‐1.201466 -‐0.415074 4 6 -‐0.634606 0.372811 -‐0.389305 5 6 -‐1.551360 1.573585 -‐0.319951 6 1 -‐3.187164 1.245035 -‐1.677278 7 1 -‐1.420070 2.059689 0.655643 8 1 -‐1.215752 2.329497 -‐1.038765 9 1 -‐3.638445 2.158146 -‐0.253807 10 1 -‐1.575534 -‐0.143198 1.899010 11 6 -‐5.026946 -‐0.280518 -‐0.626335 12 1 -‐5.743901 0.490917 -‐0.329124




SI-‐36

13 1 -‐4.971454 -‐0.281232 -‐1.718181 14 1 -‐5.416756 -‐1.251342 -‐0.304544 15 6 -‐3.591338 -‐0.286012 1.388071 16 6 -‐2.562863 0.133463 2.331447 17 6 -‐1.140616 -‐0.889979 -‐0.393104 18 1 -‐2.802260 -‐2.132821 0.135105 19 6 -‐0.280764 -‐2.140286 -‐0.367826 20 1 -‐0.400159 -‐2.617262 0.618478 21 1 -‐0.672358 -‐2.867537 -‐1.091770 22 1 -‐4.344732 -‐0.990463 1.745631 23 1 -‐2.681493 -‐0.300090 3.323493 24 1 -‐2.973342 -‐1.393919 -‐1.430437 25 6 1.204034 -‐1.870351 -‐0.632313 26 1 1.779145 -‐2.737110 -‐0.297996 27 1 1.379119 -‐1.783395 -‐1.709071 28 6 1.650032 -‐0.596006 0.097687 29 6 0.879788 0.649442 -‐0.473357 30 6 1.267262 1.890942 0.378364 31 1 0.804855 2.796912 -‐0.029060 32 1 0.872724 1.762453 1.397446 33 6 2.785687 2.095557 0.474271 34 6 3.202153 -‐0.452170 0.285937 35 6 3.481820 0.862961 1.057041 36 1 3.199070 2.342591 -‐0.510285 37 1 2.986890 2.966791 1.108050 38 1 4.565094 1.027419 1.103109 39 1 3.148048 0.733816 2.097136 40 1 1.274353 -‐0.688139 1.131159 41 6 1.155423 0.955065 -‐1.974331 42 1 0.991452 0.082812 -‐2.611032 43 1 0.489865 1.748408 -‐2.330802 44 1 2.174585 1.302499 -‐2.137582 45 6 4.013564 -‐0.495206 -‐1.028616 46 1 3.757550 -‐1.369318 -‐1.636284 47 1 3.882192 0.392955 -‐1.648988 48 1 5.081286 -‐0.566995 -‐0.795505 49 6 3.704794 -‐1.616342 1.173198 50 1 4.742488 -‐1.433650 1.471811 51 1 3.110338 -‐1.711467 2.089680 52 1 3.687761 -‐2.579403 0.653637 53 1 -‐2.513459 1.230594 2.393393 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐




SI-‐37

mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6132382 hartrees (-‐490470.123102882 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.3360303 hartrees (-‐490296.172373553 kcal/mol) D1 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.7991024 hartrees (-‐490586.754747024 kcal/mol) Imaginary Frequencies: none found Zero-‐point correction = 0.487377 (Hartree/Particle)

2.561.35

1.511.46

1.471.47

1.58

139

8

15

16

17

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 2.804206 -‐0.986640 -‐0.770363 2 6 3.271526 0.248754 -‐0.137038 3 6 2.295618 1.335800 -‐0.034469 4 6 0.395641 -‐0.262620 -‐0.284065 5 6 1.396229 -‐1.403359 -‐0.268606 6 1 2.693591 -‐0.706348 -‐1.837614 7 1 1.479860 -‐1.835909 0.737084 8 1 1.067373 -‐2.220318 -‐0.915839 9 1 3.533114 -‐1.797351 -‐0.723149 10 1 3.824415 0.133476 2.457094 11 6 5.766952 -‐0.150992 -‐0.479412 12 1 5.702833 -‐1.237022 -‐0.584315 13 1 5.773389 0.298686 -‐1.476327 14 1 6.723061 0.079304 -‐0.002157 15 6 4.634810 0.425107 0.392429 16 6 4.598998 -‐0.276025 1.804155 17 6 0.829655 1.011188 -‐0.223073 18 1 2.490521 1.928892 0.874842 19 6 -‐0.072114 2.222430 -‐0.244243 20 1 -‐0.004370 2.725168 0.733725 21 1 0.307846 2.951812 -‐0.974344




SI-‐38

22 1 4.807301 1.492418 0.573304 23 1 5.571628 -‐0.089653 2.267964 24 1 2.646668 2.032737 -‐0.831469 25 6 -‐1.536310 1.877417 -‐0.545694 26 1 -‐2.165424 2.710910 -‐0.225305 27 1 -‐1.680021 1.782950 -‐1.627019 28 6 -‐1.933194 0.578349 0.173967 29 6 -‐1.097029 -‐0.627131 -‐0.386098 30 6 -‐1.408207 -‐1.874752 0.488541 31 1 -‐0.891911 -‐2.759381 0.096469 32 1 -‐1.021970 -‐1.703621 1.503842 33 6 -‐2.912999 -‐2.166930 0.581798 34 6 -‐3.476014 0.353034 0.343058 35 6 -‐3.688366 -‐0.965662 1.131459 36 1 -‐3.303302 -‐2.459702 -‐0.399743 37 1 -‐3.067730 -‐3.033864 1.234295 38 1 -‐4.760579 -‐1.194201 1.165570 39 1 -‐3.378023 -‐0.799125 2.173276 40 1 -‐1.573118 0.686010 1.210587 41 6 -‐1.353696 -‐0.968112 -‐1.880848 42 1 -‐1.276818 -‐0.087086 -‐2.522373 43 1 -‐0.618463 -‐1.697455 -‐2.239199 44 1 -‐2.335013 -‐1.413321 -‐2.039516 45 6 -‐4.270414 0.333464 -‐0.982425 46 1 -‐4.049986 1.211480 -‐1.598844 47 1 -‐4.085036 -‐0.555071 -‐1.588458 48 1 -‐5.343883 0.353598 -‐0.765568 49 6 -‐4.056980 1.497642 1.207041 50 1 -‐5.086295 1.259157 1.495449 51 1 -‐3.481055 1.640389 2.129108 52 1 -‐4.088846 2.452338 0.672909 53 1 4.460361 -‐1.355673 1.709040 -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ mPW1PW91/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.6328007 hartrees (-‐490482.398767257 kcal/mol) MPWB1K/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.3554317 hartrees (-‐490308.346946067 kcal/mol) D2 B3LYP/6-‐31+G(d,p)//B3LYP/6-‐31+G(d,p): HF = -‐781.8048584 hartrees (-‐490590.366694584 kcal/mol) Imaginary Frequencies: none found




SI-‐39

Zero-‐point correction = 0.489272 (Hartree/Particle)

2.01

1.57

1.45

1.50

1.37

1.5184o

9

8

1516

13

17

Coordinates (from last standard orientation): -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ Center Atomic Coordinates (Angstroms) Number Number X Y Z -‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐-‐ 1 6 -‐2.574899 -‐1.718625 -‐0.285296 2 6 -‐2.886285 -‐0.292583 0.086459 3 6 -‐2.578746 0.061789 1.452875 4 6 -‐0.428357 -‐0.850078 0.528155 5 6 -‐1.248563 -‐2.116763 0.379468 6 1 -‐3.412045 -‐2.352063 0.042615 7 1 -‐0.742495 -‐2.877545 -‐0.212843 8 1 -‐1.399769 -‐2.560359 1.375287 9 1 -‐2.499539 -‐1.824612 -‐1.371134 10 1 -‐2.976797 2.579331 -‐0.152435 11 6 -‐4.941290 -‐0.110890 -‐1.257216 12 1 -‐5.468853 0.512790 -‐1.983561 13 1 -‐4.793542 -‐1.094852 -‐1.706939 14 1 -‐5.582117 -‐0.217139 -‐0.376285 15 6 -‐3.599709 0.598885 -‐0.892931 16 6 -‐3.881211 2.033947 -‐0.428502 17 6 -‐1.132780 0.271030 0.890202 18 1 -‐2.992805 0.995993 1.821976 19 6 -‐0.546518 1.665844 0.930105 20 1 -‐0.856297 2.218650 0.034318 21 1 -‐0.946000 2.214673 1.789553 22 1 -‐2.626563 -‐0.737902 2.194314 23 6 0.989834 1.625660 0.978779 24 1 1.360445 2.629560 0.759852 25 1 1.323886 1.389354 1.993991 26 6 1.535215 0.607564 -‐0.033651 27 6 1.086896 -‐0.849419 0.356748 28 6 1.538103 -‐1.828910 -‐0.763367




SI-‐40

29 1 1.321451 -‐2.862972 -‐0.473370 30 1 0.962069 -‐1.622468 -‐1.676863 31 6 3.034037 -‐1.702188 -‐1.085756 32 6 3.043969 0.799956 -‐0.421241 33 6 3.412617 -‐0.272136 -‐1.478243 34 1 3.634577 -‐2.038973 -‐0.232799 35 1 3.274958 -‐2.386731 -‐1.906665 36 1 4.487122 -‐0.212860 -‐1.688198 37 1 �

supplementary information - nature · 2014-01-23 · zheng, j., zhao, y. & truhlar, d. g....

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