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1 advances.sciencemag.org/cgi/content/full/2/8/e /dc1 Supplementary Materials for CCCCC pentadentate chelates with planar Möbius aromaticity and unique properties Congqing Zhu, Caixia Yang, Yongheng Wang, Gan Lin, Yuhui Yang, Xiaoyong Wang, Jun Zhu, Xiaoyuan Chen, Xin Lu, Gang Liu, Haiping Xia The PDF file includes: Published 26 August 2016, Sci. Adv. 2, e (2016) DOI: /sciadv Supplementary Materials and Methods fig. S1. A plausible mechanism for the formation of complex 2a from osmapentalene 1. fig. S2. The major resonance structures for the cation of 2. fig. S3. The aromaticity of model 2 evaluated by the ISE method. fig. S4. NICS(1)zz (in ppm) contributions of the MOs of model 2. fig. S5. ACID isosurfaces of the model complex 2 separated into the - contribution. fig. S6. ACID isosurfaces of the model complex 2 separated into the - contribution. fig. S7. Frontier MOs of 2a and 2c and their eigenvalues predicted at the BLYP/6-31G(d) level of theory. fig. S8. Photothermal stability of 2a. fig. S9. The average diameter of 2a@NPs confirmed by DLS and TEM. fig. S10. Photothermal effect of 2a, 2a@NPs, alkyl-pei-peg, and water under laser irradiation. fig. S11. The cytotoxicity of 2a@NPs was measured in vitro without laser irradiation. fig. S12. Pharmacological evaluation of 2a@NPs. fig. S13. Photothermal performance in vivo of 2a@NPs. fig. S14. The body weights of the mice in all groups. figs. S15 to S17. Molecular structure, selected bond distance, and angles of 2a, 2c, and 2e. figs. S18 to S22. HRMS spectra of 2a to 2e.

2 figs. S23 to S52. All NMR spectra of 2a to 2e. table S1. Crystal data and structure refinement for 2a, 2c, and 2e. data file S1. Cartesian coordinates together with the symmetry and electronic energies for all complexes calculated in this study. Other Supplementary Material for this manuscript includes the following: (available at advances.sciencemag.org/cgi/content/full/2/8/e /dc1) Data set files (.cif,.pdf)

3 Supplementary Materials and Methods Preparation of complex 2b 3-Ethynylthiophene (84 μl, 0.85 mmol) was added to a mixture of complex 1 (200 mg, 0.17 mmol) and AgBF4 (100 mg, 0.51 mmol) in dichloromethane (10 ml). The reaction mixture was stirred at RT for 5 h to yield a yellow-green solution, and then the solid suspension was removed by filtration. The filtrate was reduced under vacuum to approximately 2 ml, and then purified by column chromatography (neutral alumina, eluent: dichloromethane/methanol = 20:1) to give a green solution. The green solid of complex 2b (129 mg, 55%) was collected after the solvent was evaporated to dryness under vacuum and the resulting residue was washed with diethyl ether and then dried under vacuum. 1 H NMR plus 1 H- 13 C HSQC (500.1 MHz, CD2Cl2): δ = (d, JP-H = 26.5 Hz, 1H, H1), 8.70 (s, 1H, H3), 7.90 (s, 1H, H8), 7.76 (s, 1H, H10), 7.67 (s, 1H, H5), 7.52 (s, 1H, H6), 6.59 (s, 1H, H12), ppm (m, 51H, other aromatic protons). 31 P NMR (202.5 MHz, CD2Cl2): δ = 9.32 (t, JP-P = 5.4 Hz, CPPh3), 8.00 (dd, JP-P = Hz, JP-P = 5.4 Hz, OsPPh3), (dd, JP-P = Hz, JP-P = 5.4 Hz, OsPPh3). 13 C NMR plus DEPT-135, 1 H- 13 C HMBC and 1 H- 13 C HSQC (125.8 MHz, CD2Cl2): δ = (t, JP-C = 7.8 Hz, C7), (t, JP-C = 4.9 Hz, C11), (br, C1), (dt, JP-C = 25.6 Hz, JP-C = 5.6 Hz, C4), (s, C6), (s, C5), (s, C9), (d, JP-C = 25.5 Hz, C3), (s, C8), (d, JP-C = 86.9 Hz, C2), (s, C10), 10.0 (s, C12), 147.5, 144.3, , ppm (m, other aromatic carbons). HRMS (ESI): m/z calcd for [C74H58OsP3S2] +, ; found Anal. Calcd (%) for C74H58OsP3S2BF4: C 64.34, H 4.23; Found: C 64.24, H 4.26.

4 Preparation of complex 2c Ethynylcyclohexane (111 μl, 0.85 mmol) was added to a mixture of complex 1 (200 mg, 0.17 mmol) and AgBF4 (100 mg, 0.51 mmol) in dichloromethane (10 ml). The reaction mixture was stirred at RT for 5 h to yield a green solution, and then the solid suspension was removed by filtration. The filtrate was reduced under vacuum to approximately 2 ml, and then purified by column chromatography (neutral alumina, eluent: acetone) to give a green solution. The green solid of complex 2c (152 mg, 65%) was collected after the solvent was evaporated to dryness under vacuum and the resulting residue was washed with diethyl ether and then dried under vacuum. 1 H NMR plus 1 H- 13 C HSQC (500.1 MHz, CDCl3): δ = (d, JP-H = 22.4 Hz, 1H, H1), 8.69 (s, 1H, H3), 7.95 (s, 1H, H5), 7.58 (s, 1H, H6), 7.37 (s, 1H, H10), 7.35 (s, 1H, H8), 5.23 (s, 1H, H12), (m, 22H, C6H11), ppm (m, 45H, other aromatic protons). 31 P NMR (202.5 MHz, CDCl3): δ = 9.77 (t, JP-P = 6.7 Hz, CPPh3), (dd, JP-P = Hz, JP-P = 6.7 Hz, OsPPh3), (dd, JP-P = Hz, JP-P = 6.7 Hz, OsPPh3). 13 C NMR plus DEPT-135, 1 H- 13 C HMBC and 1 H- 13 C HSQC (125.8 MHz, CDCl3): δ = (t, JP-C = 5.9 Hz, C7), (t, JP-C = 4.2 Hz, C11), (dt, JP-C = 25.5 Hz, JP-C = 5.5 Hz, C4), (br, C1), (s, C9), (s, C6), (s, C5), (s, C3), (s, C8), (d, JP-C = 86.6 Hz, C2), (s, C10), 15.9 (s, C12), (m, C6H11), ppm (m, other aromatic carbons). HRMS (ESI): m/z calcd for [C78H74OsP3] +, ; found Anal. Calcd (%) for C78H74OsP3BF4: C 67.82, H 5.40; Found: C 67.65, H Preparation of complex 2d Cyclopropylacetylene (100 μl, 0.85 mmol) was added to a mixture of complex 1 (200 mg, 0.17

5 mmol) and AgBF4 (100 mg, 0.51 mmol) in dichloromethane (10 ml). The reaction mixture was stirred at RT for 5 h to yield a green solution, and then the solid suspension was removed by filtration. The filtrate was reduced under vacuum to approximately 2 ml, and then purified by column chromatography (neutral alumina, eluent: dichloromethane/acetone = 1:1) to give a green solution. The green solid of complex 2d (128 mg, 58%) was collected after the solvent was evaporated to dryness under vacuum and the resulting residue was washed with diethyl ether and then dried under vacuum. 1 H NMR plus 1 H- 13 C HSQC (500.1 MHz, CD2Cl2): δ = (d, JP-H = 22.0 Hz, 1H, H1), 8.47 (s, 1H, H3), 7.65 (s, 1H, H5), 7.35 (s, 1H, H6), 7.29 (s, 1H, H8), 6.75 (s, 1H, H10), 4.55 (s, 1H, H12), (m, 10H, C3H5), ppm (m, 45H, other aromatic protons). 31 P NMR (202.5 MHz, CD2Cl2): δ = 9.40 (t, JP-P = 6.5 Hz, CPPh3), (dd, JP-P = Hz, JP-P = 6.5 Hz, OsPPh3), (dd, JP-P = Hz, JP-P = 6.5 Hz, OsPPh3). 13 C NMR plus DEPT-135, 1 H- 13 C HMBC and 1 H- 13 C HSQC (125.8 MHz, CD2Cl2): δ = (t, JP-C = 8.7 Hz, C7), (t, JP-C = 4.2 Hz, C11), (dt, JP-C = 25.3 Hz, JP-C = 5.5 Hz, C4), (br, C1), (s, C9), (s, C6), (s, C5), (s, C3), (s, C8), (d, JP-C = 86.3 Hz, C2), (s, C10), 16.8 (s, C12), (m, C3H5), ppm (m, other aromatic carbons). HRMS (ESI): m/z calcd for [C72H62OsP3] +, ; found Anal. Calcd (%) for C72H62OsP3BF4: C 66.66, H 4.82; Found: C 66.88, H Preparation of complex 2e Allenylboronic acid pinacol ester (153 μl, 0.85 mmol) was added to a mixture of complex 1 (200 mg, 0.17 mmol) and AgBF4 (100 mg, 0.51 mmol) in dichloromethane (10 ml). The reaction mixture was stirred at RT for 12 h to yield a yellow solution, and then the solid suspension was removed by filtration. The filtrate was reduced under vacuum to approximately 2 ml, and then purified by column chromatography (neutral alumina, eluent: dichloromethane/acetone = 1:1) to give a yellow solution. The yellow solid of complex 2e (106 mg, 50%) was collected after the solvent was evaporated to dryness under vacuum and the resulting residue was washed with diethyl ether and then dried under vacuum. 1 H NMR plus 1 H- 13 C HSQC (500.1 MHz, CDCl3): δ = (d, JP-H = 22.1 Hz, 1H, H1), 8.74 (s, 1H, H3), 7.95 (s, 1H, H5), 7.66 (s, 1H, H6), 7.36 (s, 1H, H8), 7.09 (s, 1H, H10), 5.55 (s, 1H, H12), 2.64 (s, 3H, H14), 2.00 (s, 3H, H13), ppm (m, 45H, other aromatic protons). 31 P NMR (202.5 MHz, CDCl3): δ = 9.69 (t, JP-P = 5.4 Hz, CPPh3), 9.19 (dd, JP-P = Hz, JP-P = 5.4 Hz, OsPPh3),

6 14.41 (dd, JP-P = Hz, JP-P = 5.4 Hz, OsPPh3). 13 C NMR plus DEPT-135, 1 H- 13 C HMBC and 1 H- 13 C HSQC (125.8 MHz, CDCl3): δ = (t, JP-C = 8.2 Hz, C7), (t, JP-C = 3.4 Hz, C11), (dt, JP-C = 26.2 Hz, JP-C = 5.2 Hz, C4), (br, C1), (s, C6), (s, C9), (s, C5), (d, JP-C = 25.1 Hz, C3), (s, C8), (d, JP-C = 86.4 Hz, C2), (s, C10), 25.3 (s, C14), 21.8 (s, C13), 6.1 (s, C12), ppm (m, other aromatic carbons). HRMS (ESI): m/z calcd for [C68H58OsP3] +, ; found Anal. Calcd (%) for C68H58OsP3BF4: C 65.59, H 4.70; Found: C 65.32, H 4.76.

7 fig. S1. A plausible mechanism for the formation of complex 2a from osmapentalene 1. First, in the presence of AgBF4, the Cl ligand dissociates from osmapentalene 1 to form the intermediate A, which contains a vacant site in the osmium centre. One molecular alkyne coordinates to the osmium centre in A, leading to the formation of intermediate B. Then, the carbon-carbon triple bond of the alkyne inserts into the Os-C bond of metallacyclopropene, affording the intermediate C. The deprotonation of the intermediate C gives the intermediate D, which contains a 16-valence-electon metal centre. A second alkyne coordinates to the metal centre, and this is followed by isomerization to the Os-alkylidene intermediate F. F is subject to metal-carbene migratory insertion to form the final product 2a that contains a 2 -allene-coordinated metal centre, for which the resonance structure G can be used to represent a weak metal-allene bonding.

8 fig. S2. The major resonance structures for the cation of 2. Our experimental observations (crystal and NMR data) and theoretical calculations (NBO analyses) suggest that the resonance structures 2A-2C should be dominant, whereas 2D-2F are subordinate. fig. S3. The aromaticity of model 2' evaluated by the ISE method. The energies (in kcal mol -1, computed by the B3LYP functional with the LanL2DZ basis set for Os and the G(d,p) basis sets for C and H) include zero-point energy corrections.

9 fig. S4. NICS(1)zz (in ppm) contributions of the MOs of the model 2'. The eigenvalues of the MOs are given in parentheses, and the CMO-NICS(1)zz values of rings a, b, c, and d are given in the second line. HOMO-3 having major contribution from a d-ao of central Os atom manifests the normal d p back donation from a doubly occupied d-ao of Os to the peripheral carbon chain ligand, thus this relatively localized MO should not play an important role in the aromaticity. Similar to previous treatment, this HOMO-3 is excluded from the -MOs which contribute to the Craig-type Möbius aromaticity.

fig. S5. ACID isosurfaces of the model complex 2' separated into the -contribution. Current-density vectors are plotted onto the ACID isosurface of 0.035.

10 fig. S5. ACID isosurfaces of the model complex 2' separated into the -contribution. Current-density vectors are plotted onto the ACID isosurface of The diatropic ring current displayed in the periphery of the six-membered ring and the fused five-membered rings indicates the -aromaticity. The magnetic-field vector is orthogonal with respect to the ring plane and points upward (clockwise currents are diatropic).

fig. S6. ACID isosurfaces of the model complex 2' separated into the -contribution. Current-density vectors are plotted onto the ACID isosurface of 0.035.

11 fig. S6. ACID isosurfaces of the model complex 2' separated into the -contribution. Current-density vectors are plotted onto the ACID isosurface of The diatropic ring current only exists in the three-membered ring, indicating the -aromaticity. The magnetic-field vector is orthogonal with respect to the ring plane and points upward (clockwise currents are diatropic).

12 fig. S7. Frontier molecular orbitals of 2a and 2c and their eigenvalues predicted at the BLYP/6-31G(d) level of theory.

13 fig. S8. Photothermal stability of 2a. To assess the NIR photostability of 2a in chloroform (0.2 mg ml -1 ), six laser on off cycles were performed by irradiating the solution of 2a with an 808-nm laser for 10 min (laser on), followed by allowing the solution to cool to room temperature for 30 min (laser off). No significant change in the temperature increase was observed after six cycles (a). We also compared the absorption spectra (b) and HRMS spectra (c) of the sample before and after the NIR laser irradiation for six laser on off cycles. These results show that there is no significant decomposition, which suggests that 2a exhibit good photothermal stability under the laser irradiation conditions.

fig. S9. The average diameter of 2a@NPs confirmed by DLS and TEM. a) DLS measured sizes of synthetic 2a@NPs in aqueous solutions. b) TEM image of 2a@NPs.

14 fig. S9. The average diameter of confirmed by DLS and TEM. a) DLS measured sizes of synthetic in aqueous solutions. b) TEM image of This larger size observed by DLS (approximately 70 nm) compared to that measured from SEM (50 nm, on average) is attributed to the swelling of the nanoparticles under aqueous conditions. fig. S10. Photothermal effect of 2a, Alkyl-PEI-PEG, and water under laser irradiation. To investigate the photothermal performance of this nanoparticle, the aqueous solution of (containing 0.1 mg ml -1 2a) was exposed to an NIR laser beam. The temperature of this solution was elevated by 25 C after laser irradiation for 10 min, which was equal to the temperature increase of 2a. The concentrations of 2a were 0.10 mg ml -1.

fig. S11. The cytotoxicity of the 2a@NPs was measured in vitro without laser irradiation.

The cytotoxicity of the 2a@NPs was assessed using a standard MTT assay on SCC7, SCG79011, and 4T1 cancer cells. With the concentration of 2a ranging from 0.01 to 0.

15 fig. S11. The cytotoxicity of the was measured in vitro without laser irradiation. Relative cell viability of SCC7, SCG79011, and 4T1 cells incubated under different concentrations of for 5 h. The cytotoxicity of the 2a@NPs was assessed using a standard MTT assay on SCC7, SCG79011, and 4T1 cancer cells. With the concentration of 2a ranging from 0.01 to 0.10 mg ml -1 in 2a@NPs, all of the cells retained greater than 90% viability, indicating that the 2a@NPs exhibit low cell cytotoxicity. fig. S12. Pharmacological evaluation of 2a@NPs in SCC7 tumor-bearing mice treated with 2a@NPs (7.3 nmol kg -1 ). a) Dynamic IR thermal images of a SCC7 tumor-bearing mouse exposed to the 808 nm NIR laser (1 W cm -2 ). The SI reached the maximum in the tumor rim at 5 h post-injection. b) The significant accumulation of 2a@NPs was observed in the tumor tissue and clearance organs including liver and spleen.

fig. S13. Photothermal performance in vivo of 2a@NPs.

The temperature of tumors treated with 2a@NPs increased gradually and reached approximately 52 C after 10 min of NIR laser irradiation, whereas the tumors injected with

16 fig. S13. Photothermal performance in vivo of Tumor temperatures of mice were monitored by an IR thermal camera under laser irradiation (1 W cm -2 ) at 5 h post-injection. The temperature of tumors treated with 2a@NPs increased gradually and reached approximately 52 C after 10 min of NIR laser irradiation, whereas the tumors injected with saline exhibited no significant temperature increase (less than 40 C) during this process, suggesting the excellent photothermal performance of 2a@NPs in vivo. fig. S14. The body weights of the mice in all groups. Body weights of mice in the groups of saline with laser, saline without laser, 2a@NPs with laser, and 2a@NPs without laser.

17 fig. S15. X-ray molecular structure of the cation of complex 2a. The phenyl rings of the PPh3 ligands have been omitted for clarity. Thermal ellipsoids of the remaining non-hydrogen atoms are drawn at 50% probability. Selected bond distances (Å) and angles (deg): Os1 C (4), Os1 C (4), Os1 C (4), Os1 C (4), Os1 C (4), C1 C (6), C2 C (6), C3 C (6), C4 C (5), C5 C (6), C6 C (5), C7 C (5), C8 C (5), C9 C (5), C10 C (6), C11 C (5), Os1 C1 C (3), C1 C2 C (4), C2 C3 C (4), C3 C4 Os (3), C4 Os1 C (15), Os1 C4 C (3), C4 C5 C (3), C5 C6 C (4), C6 C7 Os (3), C7 Os1 C (15), Os1 C7 C (3), C7 C8 C (4), C8 C9 C (4), C9 C10 C (4), C10 C11 Os (3), C11 Os1 C (15), Os1 C11 C (2), C11 C12 Os1 62.2(2), C12 Os1 C (14).

18 fig. S16. X-ray molecular structure of the cation of complex 2c. The phenyl rings of the PPh3 ligands have been omitted for clarity. Thermal ellipsoids of the remaining non-hydrogen atoms are drawn at 50% probability. Selected bond distances (Å) and angles (deg): Os1 C (6), Os1 C (5), Os1 C (6), Os1 C (6), Os1 C (5), C1 C (8), C2 C (8), C3 C (8), C4 C (8), C5 C (8), C6 C (8), C7 C (8), C8 C (8), C9 C (8), C10 C (8), C11 C (8), Os1 C1 C (4), C1 C2 C (5), C2 C3 C (5), C3 C4 Os (4), C4 Os1 C1 74.8(2), Os1 C4 C (4), C4 C5 C (5), C5 C6 C (6), C6 C7 Os (4), C7 Os1 C4 77.0(2), Os1 C7 C (5), C7 C8 C (6), C8 C9 C (6), C9 C10 C (5), C10 C11 Os (4), C11 Os1 C7 81.4(2), Os1 C11 C (3), C11 C12 Os1 63.9(3), C12 Os1 C (2).

19 fig. S17. X-ray molecular structure of the cation of complex 2e. The phenyl rings of the PPh3 ligands have been omitted for clarity. Thermal ellipsoids of the remaining non-hydrogen atoms are drawn at 50% probability. Selected bond distances (Å) and angles (deg): Os1 C (6), Os1 C (6), Os1 C (5), Os1 C (6), Os1 C (7), C1 C (8), C2 C (8), C3 C (7), C4 C (7), C5 C (8), C6 C (8), C7 C (7), C8 C (8), C9 C (8), C10 C (8), C11 C (8), Os1 C1 C (4), C1 C2 C (5), C2 C3 C (5), C3 C4 Os (4), C4 Os1 C1 75.4(2), Os1 C4 C (4), C4 C5 C (6), C5 C6 C (5), C6 C7 Os (4), C7 Os1 C4 77.8(2), Os1 C7 C (5), C7 C8 C (5), C8 C9 C (6), C9 C10 C (6), C10 C11 Os (5), C11 Os1 C7 81.4(2), Os1 C11 C (4), C11 C12 Os1 63.5(4), C12 Os1 C (2).

20 fig. S18. Positive-ion ESI-MS spectrum of [2a] + [C78H62OsP3] + measured in methanol.

21 fig. S19. Positive-ion ESI-MS spectrum of [2b] + [C74H58OsP3S2] + measured in methanol.

22 fig. S20. Positive-ion ESI-MS spectrum of [2c] + [C78H74OsP3] + measured in methanol.

23 fig. S21. Positive-ion ESI-MS spectrum of [2d] + [C72H62OsP3] + measured in methanol.

24 fig. S22. Positive-ion ESI-MS spectrum of [2e] + [C68H58OsP3] + measured in methanol.

25 fig. S P NMR spectrum (202.5 MHz) of complex 2a in CD2Cl2 at room temperature. fig. S24. 1 H NMR spectrum (500.1 MHz) of complex 2a in CD2Cl2 at room temperature (inset: partial 1 H- 13 C HSQC spectrum for complex 2a).

26 fig. S C NMR spectrum (125.8 MHz) of complex 2a in CD2Cl2 at room temperature. fig. S26. DEPT-135 spectrum (125.8 MHz) of complex 2a in CD2Cl2 at room temperature.

27 fig. S27. Two-dimensional 1 H- 13 C HSQC spectrum of complex 2a in CD2Cl2 at room temperature.

28 fig. S28. Two-dimensional 1 H- 13 C HMBC spectrum of complex 2a in CD2Cl2 at room temperature.

29 fig. S P NMR spectrum (202.5 MHz) of complex 2b in CD2Cl2 at room temperature. fig. S30. 1 H NMR spectrum (500.1 MHz) of complex 2b in CD2Cl2 at room temperature (inset: partial 1 H- 13 C HSQC spectrum for complex 2b).

30 fig. S C NMR spectrum (125.8 MHz) of complex 2b in CD2Cl2 at room temperature. fig. S32. DEPT-135 spectrum (125.8 MHz) of complex 2b in CD2Cl2 at room temperature.

31 fig. S33. Two-dimensional 1 H- 13 C HSQC spectrum of complex 2b in CD2Cl2 at room temperature.

32 fig. S34. Two-dimensional 1 H- 13 C HMBC spectrum of complex 2b in CD2Cl2 at room temperature.

33 fig. S P NMR spectrum (202.5 MHz) of complex 2c in CDCl3 at room temperature. fig. S36. 1 H NMR spectrum (500.1 MHz) of complex 2c in CDCl3 at room temperature (inset: partial 1 H- 13 C HSQC spectrum for complex 2c).

34 fig. S C NMR spectrum (125.8 MHz) of complex 2c in CDCl3 at room temperature. fig. S38. DEPT-135 spectrum (125.8 MHz) of complex 2c in CDCl3 at room temperature.

35 fig. S39. Two-dimensional 1 H- 13 C HSQC spectrum of complex 2c in CDCl3 at room temperature. fig. S40. Two-dimensional 1 H- 13 C HMBC spectrum of complex 2c in CDCl3 at room temperature.

36 fig. S P NMR spectrum (202.5 MHz) of complex 2d in CD2Cl2 at room temperature. fig. S42. 1 H NMR spectrum (500.1 MHz) of complex 2d in CD2Cl2 at room temperature (inset: partial 1 H- 13 C HSQC spectrum for complex 2d).

37 fig. S C NMR spectrum (125.8 MHz) of complex 2d in CD2Cl2 at room temperature. fig. S44. DEPT-135 spectrum (125.8 MHz) of complex 2d in CD2Cl2 at room temperature.

38 fig. S45. Two-dimensional 1 H- 13 C HSQC spectrum of complex 2d in CD2Cl2 at room temperature.

39 fig. S46. Two-dimensional 1 H- 13 C HMBC spectrum of complex 2d in CD2Cl2 at room temperature.

40 fig. S P NMR spectrum (202.5 MHz) of complex 2e in CDCl3 at room temperature. fig. S48. 1 H NMR spectrum (500.1 MHz) of complex 2e in CDCl3 at room temperature (inset: partial 1 H- 13 C HSQC spectrum for complex 2e).

41 fig. S C NMR spectrum (125.8 MHz) of complex 2e in CDCl3 at room temperature. fig. S50. DEPT-135 spectrum (125.8 MHz) of complex 2e in CDCl3 at room temperature.

42 fig. S51. Two-dimensional 1 H- 13 C HSQC spectrum of complex 2e in CDCl3 at room temperature.

43 fig. S52. Two-dimensional 1 H- 13 C HMBC spectrum of complex 2e in CDCl3 at room temperature.

44 table S1. Crystal data and structure refinement for 2a, 2c, and 2e. 2a CH 2Cl 2 0.5H 2O 2c 2e CH 2Cl 2 empirical formula [C 78H 62OsP 3]BF 4 CH 2Cl 2 0.5H 2O [C 78H 74OsP 3]BF 4 2[C 68H 58OsP 3]2BF 4 CH 2Cl 2 formula weight temperature, K 173(2) 173(2) 173(2) radiation (Mo K ), Å crystal system Monoclinic Monoclinic Triclinic space group C2/c P2 1/c P-1 a, Å (8) (3) 9.938(2) b, Å (3) (4) (5) c, Å (5) (5) (5), (3) β, 90.15(3) 96.12(3) 96.47(3) γ, (3) V, Å (5) 6370(2) 5699(2) Z d calcd, g cm μ(mo Kα), mm F(000) crystal size, mm θ max, reflns collected indep reflns data/restraints/params 11520/30/ /0/ /0/1414 goodness-of-fit on F final R (I > 2σ(I)) R 1 = wr 2 = R 1 = , wr 2 = R 1 = wr 2 =

45 R indices (all data) R 1 = wr 2 = R 1 = wr 2 = R 1 = wr 2 = Residual electron density (e. Å -3 ) max/min 1.607/ / /-2.261

46 Cartesian coordinates together with the symmetry and electronic energies for all complexes calculated in this study: E = E = Os P P C C H C C C H C H C H C C H C H H H H H H H H H C C H H Os P P C C C C C C C C C H C H H H H H H C C H H H H H H H C C C H H

47 H H H E = E = Os P P C C C C C C C C C H C H H H H H H C C H H H H H H H C H C C H H Os P P C C H C C C C H C C C H C H H H H H H H C C H H H H C C C H H H H

48 E = Os P P C C H C C C C H C C C H C H H H H H H H C C H H H H C H C C H H H E = Os P P C C H C C C H C H C C C C H H H H H H H H C C H H C H C C H H H H

49 E = Os P P C C H C C C H C H C C C C H H H H H H H H C C H H C H H C C H H H E = Os P P C C H C C C C C C C C H H H H H H C C H H C H H C C H C C H C H C C

50 H C H H H H H H H H H H H H C C H H C H H C C H C E = Os P P C C H C C C C C C C C H H C H C H C C H C H H H H H H

David L. Davies,, 1 Charles E. Ellul, 1 Stuart A. Macgregor,, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information

David L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information Experimental Supporting Information for Experimental and DFT Studies Explain Solvent Control of C-H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of eutral and Cationic Heterocycles