Title N-H versus C-H Activation of a Pyrrole Imine at {Cp*Ir}: A Computational and Experimental Study

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1 Supporting Information for: Title N-H versus C-H Activation of a Pyrrole Imine at {Cp*Ir}: A Computational and Experimental Study David L. Davies,* a Steven M. A. Donald, b Omar Al-Duaij, a John Fawcett, a Craig Little b and Stuart A. Macgregor* b a Department of Chemistry, University of Leicester, Leicester,LE1 7RH U.K. b School of Engineering and Physical Sciences, William Perkin Building, Heriot-Watt University Edinburgh EH14 4AS, U.K.. Contents: Full Reference 13 Tables of Cartesian Coordinates (Å) and Computed Energies (a.u.) for all Stationary Points. Experimental procedure and spectroscopic data for 1a and 2 Tables of crystallographic data, bond lengths and angles for 1a and 2. S1

2 Full Reference 13. Gaussian 03, Revision C.02 1 and employed the BP86 functional. Ir and Cl were described using the Stuttgart RECPs and the associated basis sets 2 and a polarisation function was added for Cl (ζ = 0.640) G** basis sets were used for C, N, O and H atoms. 4 All stationary points were characterised via analytical frequency calculations which furnished the zero-point energy corrections that are included in the figures quoted in the text. 1. Gaussian 03, Revision C.02, 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, 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, Andrae, D.; Häusserman, U.; Dolg, M.; Stoll, H.; Preuss, Η. Theor. Chim. Acta 1990, 77, Höllwarth, A.; Böhme, M.; Dapprich, S.; Ehlers, A. W.; Gobbi, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213. S2

3 3 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C N C C C Ir N C C C C C C O H H H H H H H H H H C C H H H O H S3

4 TS 3-5 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = Nimag = 1 ( cm -1 ) C N C C C Ir N C C C C C C O H H H H H H H H H H C C H H H O H S4

5 5 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C N C C C Ir N C C C C C C O C C O H H H H H H H H H H H H H H S5

6 4 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C C C N C Ir N C C C C C C O H H H H H H H H H H C C H H H O H S6

7 TS 4-6 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = Nimag = 1 ( cm -1 ) C C C N C Ir N C C C C C C O H H H H H H H H H H C C H H H O H S7

8 6 Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C C C N C Ir N C C C C C C O C C O H H H H H H H H H H H H H H S8

9 [IrCl(Cp)(κ N,N NH=CH-NC 4 H 3 )] Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C C C C C Ir N C C C C Cl N C H H H H H H H H H H S9

10 [IrCl(Cp)(κ N,C NH=CH-NC 4 H 3 )] Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = C C C C C Ir C C N C C Cl N C H H H H H H H H H H S10

11 4-membered C-H activation TS ( σ-bond metathesis ) Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = Nimag = 1 ( cm -1 ) C C C C C Ir C C N C C O N C H H H H H H H H H H C O C H H H H S11

12 4-membered N-H activation TS ( σ-bond metathesis ) Energy = Enthalpy (0K) = Enthalpy ( K) = Free Energy = Nimag = 1 ( cm -1 ) C C C C C Ir N C C C C O N C H H H H H H H H H H C O C H H H H S12

13 Experimental procedures and spectroscopic information for 1a and 2 [IrCl{C 4 H 3 N-2-C(H)=N(3,5-Me 2 C 6 H 3 )- K N,N}(η-C 5 Me 5 )] (1a) NaOAc (27 mg, 0.33 mmol) and [IrCl 2 Cp*] 2 (105 mg, 0.13 mmol) were added to a solution of pyrrole imine L1 (53 mg, 0.26 mmol) in dichloromethane and the mixture was stirred at room temperature overnight. The mixture was filtered through Celite and the filtrate was evaporated to dryness and the solid was washed with hexane to remove any unreacted ligand and dried under vacuum. The Me Me 11 N Ir 12 Cl N complex 1a was isolated as a yellow precipitate (120 mg, 81%), it could be recrystallised from dichloromethane / hexane. Calc. for C 23 H 28 N 2 ClIr: C, 49.32, H, 5.04, N, Found: C, 49.22, H, 4.90, N, 4.95%. 1 H NMR (CDCl 3, 300 MHz): δ 1.50 (s, 15H, Cp*), 2.33 (s, 6H, 2x Me), 6.38 (dd, 1H, J 3.5, 1.5, H 4 ), 6.78 (d, 1H, J 3.5, H 3 ), 6.86 (s, 1H, H 10 ), 7.11 (s, 2H, H 8, H 12 ), 7.17 (br s, 1H, H 5 ), 7.74 (s, 1H, HC=N). 13 C NMR: δ 8.85 (C 5 Me 5 ), (2x Me), (C 5 Me 5 ), (C 4 ), (C 3 ), (C 8, C 12 ), (C 10 ), (C 5 ), (C 9, C 11 ), (C 2 ), (C 7 ), (C 6 ). MS (FAB): m/z 560 [M] +, 525 [M-Cl] +. [IrCl{C 4 H 2 N-3-CH 3-2-C(H)=N(3,5-Me 2 C 6 H 3 )- k C,N}(η-C 5 Me 5 )] (2) This was prepared in a similar manner from NaOAc (19 mg, Me 0.23 mmol), [IrCl 2 Cp*] 2 (70 mg, 0.09 mmol), and pyrrole imine L2 (38 mg, 0.18 mmol); after stirring for 4 hours, 2 was isolated 7 Me as a brown precipitate and recrystallised from dichloromethane / N hexane (88 mg, 88%). Calc. for C 24 H 30 N 2 ClIr: C, 50.20, H, 5.27, N, Found: C, 50.12, H, 5.30, N, 4.87%. 1 H NMR: δ 1.54 (s, 15H, Cp*), 2.33 (s, 6H, 2x Me), 3.78 (s, 3H, NMe), 6.41 (d, 1H, 6 Me 2 J 2, H 5 ), 6.78 (d, 1H, J 2, H 4 ), 6.82 (s, 1H, H 10 ), 7.14 (s, 2H, H 8, H 12 ), 7.79 (s, 1H, HC=N). 13 C NMR: δ 9.21 (C 5 Me 5 ), (2x Me), (NMe) (C 5 Me 5 ), (C 5 ), (C 8, C 12 ), (C 10 ), (C 4 ), (C 9, C 11 ), (C 2 ), (C 7 ), (C 6 ), (C 1 ). MS (FAB): m/z 574 [M] +, 539 [M-Cl] +. ν(c=n) 1610 cm Ir 12 Cl 1 N 5 4 S13

14 Table 1. Crystal data and structure refinement for 1a (ID code 03008). Identification code Empirical formula C23 H28 Cl Ir N2 Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = (8) Å α= 90. b = 8.143(4) Å β= (7). c = (8) Å γ = 90. Volume (17) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1096 Crystal size 0.38 x 0.12 x 0.10 mm 3 Theta range for data collection 1.33 to Index ranges -20<=h<=20, -10<=k<=10, -20<=l<=20 Reflections collected Independent reflections 4110 [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission 0.58 and 0.22 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4110 / 0 / 251 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S14

15 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Ir(1) 7226(1) 2944(1) 5997(1) 20(1) Cl(1) 6626(1) 5156(1) 6541(1) 31(1) N(1) 8258(2) 2996(3) 7171(2) 23(1) N(2) 8089(2) 4719(4) 5823(2) 20(1) C(1) 8449(3) 2305(5) 7938(3) 29(1) C(2) 9260(3) 2896(5) 8511(3) 34(1) C(3) 9561(2) 4011(5) 8071(3) 31(1) C(4) 8928(2) 4062(4) 7233(2) 24(1) C(5) 8798(2) 4967(4) 6489(2) 22(1) C(6) 7958(2) 5591(4) 5054(2) 22(1) C(7) 8639(2) 5795(4) 4763(2) 23(1) C(8) 8513(3) 6667(5) 4024(3) 25(1) C(9) 7691(3) 7327(5) 3563(3) 26(1) C(10) 6998(3) 7126(4) 3836(3) 25(1) C(11) 7134(2) 6259(4) 4589(3) 24(1) C(12) 9253(3) 6902(5) 3716(3) 33(1) C(13) 6120(3) 7872(5) 3341(3) 35(1) C(14) 7211(3) 1147(5) 5062(3) 31(1) C(15) 7228(2) 336(5) 5819(3) 26(1) C(16) 6454(2) 815(4) 5981(3) 25(1) C(17) 5942(3) 1858(4) 5285(3) 26(1) C(18) 6392(3) 2073(4) 4716(3) 30(1) C(19) 7869(4) 1072(6) 4650(4) 54(1) C(20) 7905(3) -847(5) 6362(3) 42(1) C(21) 6199(3) 194(5) 6674(3) 38(1) C(22) 5088(3) 2573(6) 5190(3) 39(1) C(23) 6044(4) 2903(5) 3858(3) 49(2) S15

16 Table 3. Bond lengths [Å] and angles [ ] for Ir(1)-N(1) 2.069(3) Ir(1)-N(2) 2.123(3) Ir(1)-C(14) 2.143(4) Ir(1)-C(16) 2.144(4) Ir(1)-C(15) 2.145(4) Ir(1)-C(17) 2.191(4) Ir(1)-C(18) 2.198(5) Ir(1)-Cl(1) (12) N(1)-C(1) 1.335(5) N(1)-C(4) 1.378(5) N(2)-C(5) 1.298(4) N(2)-C(6) 1.421(5) C(1)-C(2) 1.408(6) C(2)-C(3) 1.376(6) C(3)-C(4) 1.408(5) C(4)-C(5) 1.398(5) C(6)-C(7) 1.393(5) C(6)-C(11) 1.399(5) C(7)-C(8) 1.379(5) C(8)-C(9) 1.394(6) C(8)-C(12) 1.505(6) C(9)-C(10) 1.392(6) C(10)-C(11) 1.394(6) C(10)-C(13) 1.501(6) C(14)-C(15) 1.427(6) C(14)-C(18) 1.464(6) C(14)-C(19) 1.490(6) C(15)-C(16) 1.454(5) C(15)-C(20) 1.498(5) C(16)-C(17) 1.437(5) C(16)-C(21) 1.471(5) C(17)-C(18) 1.424(6) C(17)-C(22) 1.475(6) C(18)-C(23) 1.502(6) N(1)-Ir(1)-N(2) 76.39(12) S16

17 N(1)-Ir(1)-C(14) (14) N(2)-Ir(1)-C(14) (13) N(1)-Ir(1)-C(16) (14) N(2)-Ir(1)-C(16) (13) C(14)-Ir(1)-C(16) 66.09(15) N(1)-Ir(1)-C(15) 96.35(13) N(2)-Ir(1)-C(15) (13) C(14)-Ir(1)-C(15) 38.87(15) C(16)-Ir(1)-C(15) 39.61(13) N(1)-Ir(1)-C(17) (14) N(2)-Ir(1)-C(17) (14) C(14)-Ir(1)-C(17) 65.08(16) C(16)-Ir(1)-C(17) 38.70(14) C(15)-Ir(1)-C(17) 64.87(14) N(1)-Ir(1)-C(18) (14) N(2)-Ir(1)-C(18) (15) C(14)-Ir(1)-C(18) 39.39(16) C(16)-Ir(1)-C(18) 64.90(16) C(15)-Ir(1)-C(18) 64.93(14) C(17)-Ir(1)-C(18) 37.87(17) N(1)-Ir(1)-Cl(1) 85.92(9) N(2)-Ir(1)-Cl(1) 86.24(9) C(14)-Ir(1)-Cl(1) (12) C(16)-Ir(1)-Cl(1) (11) C(15)-Ir(1)-Cl(1) (11) C(17)-Ir(1)-Cl(1) 93.45(11) C(18)-Ir(1)-Cl(1) (13) C(1)-N(1)-C(4) 107.5(3) C(1)-N(1)-Ir(1) 136.7(3) C(4)-N(1)-Ir(1) 115.7(3) C(5)-N(2)-C(6) 119.4(3) C(5)-N(2)-Ir(1) 114.8(2) C(6)-N(2)-Ir(1) 125.8(2) N(1)-C(1)-C(2) 109.7(4) C(3)-C(2)-C(1) 107.4(4) C(2)-C(3)-C(4) 106.1(4) N(1)-C(4)-C(5) 114.5(3) N(1)-C(4)-C(3) 109.3(4) S17

18 C(5)-C(4)-C(3) 136.1(4) N(2)-C(5)-C(4) 118.6(3) C(7)-C(6)-C(11) 119.9(3) C(7)-C(6)-N(2) 120.8(3) C(11)-C(6)-N(2) 119.3(3) C(8)-C(7)-C(6) 120.7(3) C(7)-C(8)-C(9) 119.2(4) C(7)-C(8)-C(12) 120.6(4) C(9)-C(8)-C(12) 120.3(4) C(10)-C(9)-C(8) 121.2(4) C(9)-C(10)-C(11) 119.1(4) C(9)-C(10)-C(13) 120.6(4) C(11)-C(10)-C(13) 120.3(4) C(10)-C(11)-C(6) 119.9(4) C(15)-C(14)-C(18) 107.5(4) C(15)-C(14)-C(19) 128.4(4) C(18)-C(14)-C(19) 124.0(4) C(15)-C(14)-Ir(1) 70.6(2) C(18)-C(14)-Ir(1) 72.3(2) C(19)-C(14)-Ir(1) 124.0(3) C(14)-C(15)-C(16) 108.5(3) C(14)-C(15)-C(20) 127.2(4) C(16)-C(15)-C(20) 124.3(4) C(14)-C(15)-Ir(1) 70.5(2) C(16)-C(15)-Ir(1) 70.2(2) C(20)-C(15)-Ir(1) 126.2(3) C(17)-C(16)-C(15) 107.2(3) C(17)-C(16)-C(21) 126.5(4) C(15)-C(16)-C(21) 126.0(4) C(17)-C(16)-Ir(1) 72.4(2) C(15)-C(16)-Ir(1) 70.2(2) C(21)-C(16)-Ir(1) 127.8(3) C(18)-C(17)-C(16) 109.0(4) C(18)-C(17)-C(22) 126.4(4) C(16)-C(17)-C(22) 124.6(4) C(18)-C(17)-Ir(1) 71.3(2) C(16)-C(17)-Ir(1) 68.9(2) C(22)-C(17)-Ir(1) 125.9(3) S18

19 C(17)-C(18)-C(14) 107.7(4) C(17)-C(18)-C(23) 126.6(5) C(14)-C(18)-C(23) 125.3(5) C(17)-C(18)-Ir(1) 70.8(2) C(14)-C(18)-Ir(1) 68.3(2) C(23)-C(18)-Ir(1) 132.3(3) Symmetry transformations used to generate equivalent atoms: S19

20 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Ir(1) 21(1) 21(1) 18(1) -1(1) 7(1) -1(1) Cl(1) 29(1) 33(1) 30(1) -9(1) 10(1) 3(1) N(1) 23(2) 26(2) 18(2) 3(1) 5(1) 2(1) N(2) 19(2) 22(1) 18(2) 0(1) 6(1) 0(1) C(1) 38(2) 32(2) 17(2) 3(2) 9(2) 3(2) C(2) 34(3) 42(3) 19(2) 5(2) 4(2) 12(2) C(3) 22(2) 41(2) 25(2) -2(2) 2(2) 6(2) C(4) 19(2) 28(2) 23(2) 0(2) 4(2) 6(2) C(5) 18(2) 23(2) 26(2) -2(2) 10(2) -3(1) C(6) 26(2) 20(2) 19(2) -5(2) 6(2) -3(2) C(7) 23(2) 22(2) 21(2) -2(2) 5(2) -1(1) C(8) 34(2) 21(2) 23(2) -3(2) 14(2) -2(2) C(9) 30(2) 26(2) 20(2) 2(2) 8(2) 2(2) C(10) 26(2) 25(2) 20(2) -2(2) 4(2) 2(2) C(11) 24(2) 23(2) 27(2) 0(2) 11(2) 0(2) C(12) 32(2) 37(2) 31(3) 5(2) 15(2) -1(2) C(13) 30(2) 45(3) 27(3) 9(2) 7(2) 10(2) C(14) 42(2) 25(2) 30(2) -11(2) 19(2) -11(2) C(15) 21(2) 22(2) 32(2) -4(2) 7(2) -3(2) C(16) 22(2) 21(2) 30(2) -1(2) 9(2) -2(1) C(17) 23(2) 25(2) 24(2) 0(2) 4(2) -5(2) C(18) 39(3) 27(2) 20(2) -3(2) 6(2) -11(2) C(19) 70(3) 48(3) 65(4) -26(3) 48(3) -20(3) C(20) 30(2) 30(2) 60(3) -1(2) 9(2) 5(2) C(21) 45(3) 38(2) 31(2) 7(2) 16(2) -8(2) C(22) 28(2) 35(2) 47(3) -5(2) 6(2) -3(2) C(23) 74(4) 41(3) 20(3) -2(2) 3(3) -20(2) S20

21 Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for x y z U(eq) H(1) H(2) H(3) H(5) H(7) H(9) H(11) H(12A) H(12B) H(12C) H(13A) H(13B) H(13C) H(19A) H(19B) H(19C) H(20A) H(20B) H(20C) H(21A) H(21B) H(21C) H(22A) H(22B) H(22C) H(23A) H(23B) H(23C) S21

22 Table 1. Crystal data and structure refinement for 2 (ID code 03069). Identification code Empirical formula C24 H30 Cl Ir N2 Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = (4) Å α= 90. b = (9) Å β= (2). c = (17) Å γ = 90. Volume (8) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2256 Crystal size 0.21 x 0.19 x 0.06 mm 3 Theta range for data collection 2.34 to Index ranges -45<=h<=46, -10<=k<=10, -18<=l<=18 Reflections collected Independent reflections 4286 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4286 / 0 / 261 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S22

23 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Ir(1) 1064(1) 3242(1) -32(1) 21(1) Cl(1) 1100(1) 5726(1) 824(1) 31(1) N(1) 53(1) 2278(6) 335(3) 36(1) N(2) 1088(1) 1975(4) 1176(3) 24(1) C(1) 504(2) 3096(5) -218(3) 26(1) C(2) 144(2) 3606(7) -836(4) 36(1) C(3) -124(2) 3105(7) -476(4) 43(2) C(4) -131(2) 1587(9) 920(5) 59(2) C(5) 439(2) 2279(6) 503(4) 30(1) C(6) 760(2) 1676(5) 1253(4) 28(1) C(7) 1436(2) 1400(6) 1878(3) 26(1) C(8) 1726(2) 2514(6) 2328(3) 27(1) C(9) 2075(2) 1987(6) 2987(3) 28(1) C(10) 2126(2) 321(6) 3165(3) 32(1) C(11) 1846(2) -804(6) 2712(3) 28(1) C(12) 1497(1) -252(6) 2066(3) 28(1) C(13) 2392(2) 3182(6) 3476(4) 37(1) C(14) 1916(2) -2605(6) 2882(4) 38(1) C(15) 1604(2) 2504(6) -225(3) 29(1) C(16) 1281(2) 1447(6) -716(4) 28(1) C(17) 992(2) 2414(6) -1410(3) 28(1) C(18) 1120(2) 4072(6) -1296(3) 28(1) C(19) 1504(2) 4087(6) -582(3) 28(1) C(20) 1984(2) 1952(7) 478(4) 39(1) C(21) 1282(2) -354(6) -617(4) 41(1) C(22) 629(2) 1803(7) -2136(4) 42(2) C(23) 918(2) 5484(7) -1913(4) 41(1) C(24) 1743(2) 5580(7) -260(4) 40(1) S23

24 Table 3. Bond lengths [Å] and angles [ ] for Ir(1)-C(1) 2.019(5) Ir(1)-N(2) 2.094(4) Ir(1)-C(17) 2.133(4) Ir(1)-C(18) 2.136(5) Ir(1)-C(16) 2.139(5) Ir(1)-C(19) 2.234(5) Ir(1)-C(15) 2.244(5) Ir(1)-Cl(1) (11) N(1)-C(3) 1.346(7) N(1)-C(5) 1.374(6) N(1)-C(4) 1.440(7) N(2)-C(6) 1.304(7) N(2)-C(7) 1.421(6) C(1)-C(2) 1.386(7) C(1)-C(5) 1.390(7) C(2)-C(3) 1.384(8) C(5)-C(6) 1.402(7) C(7)-C(12) 1.383(7) C(7)-C(8) 1.385(7) C(8)-C(9) 1.386(7) C(9)-C(10) 1.389(6) C(9)-C(13) 1.501(7) C(10)-C(11) 1.372(7) C(11)-C(12) 1.385(7) C(11)-C(14) 1.502(7) C(15)-C(19) 1.400(7) C(15)-C(16) 1.447(7) C(15)-C(20) 1.494(7) C(16)-C(17) 1.434(7) C(16)-C(21) 1.481(7) C(17)-C(18) 1.428(7) C(17)-C(22) 1.482(7) C(18)-C(19) 1.441(7) C(18)-C(23) 1.502(7) C(19)-C(24) 1.486(7) S24

25 C(1)-Ir(1)-N(2) 77.68(18) C(1)-Ir(1)-C(17) 96.32(19) N(2)-Ir(1)-C(17) (18) C(1)-Ir(1)-C(18) (19) N(2)-Ir(1)-C(18) (17) C(17)-Ir(1)-C(18) 39.07(19) C(1)-Ir(1)-C(16) (19) N(2)-Ir(1)-C(16) (16) C(17)-Ir(1)-C(16) 39.23(19) C(18)-Ir(1)-C(16) 65.56(18) C(1)-Ir(1)-C(19) (19) N(2)-Ir(1)-C(19) (17) C(17)-Ir(1)-C(19) 63.75(19) C(18)-Ir(1)-C(19) 38.42(18) C(16)-Ir(1)-C(19) 63.33(17) C(1)-Ir(1)-C(15) (19) N(2)-Ir(1)-C(15) (17) C(17)-Ir(1)-C(15) 64.16(18) C(18)-Ir(1)-C(15) 63.84(18) C(16)-Ir(1)-C(15) 38.45(19) C(19)-Ir(1)-C(15) 36.43(18) C(1)-Ir(1)-Cl(1) 88.07(13) N(2)-Ir(1)-Cl(1) 87.80(10) C(17)-Ir(1)-Cl(1) (14) C(18)-Ir(1)-Cl(1) (13) C(16)-Ir(1)-Cl(1) (15) C(19)-Ir(1)-Cl(1) 92.75(12) C(15)-Ir(1)-Cl(1) (14) C(3)-N(1)-C(5) 106.8(5) C(3)-N(1)-C(4) 125.8(5) C(5)-N(1)-C(4) 127.3(5) C(6)-N(2)-C(7) 120.1(4) C(6)-N(2)-Ir(1) 116.6(3) C(7)-N(2)-Ir(1) 123.3(3) C(2)-C(1)-C(5) 105.4(5) C(2)-C(1)-Ir(1) 140.5(4) C(5)-C(1)-Ir(1) 114.0(4) C(3)-C(2)-C(1) 108.0(5) S25

26 N(1)-C(3)-C(2) 109.7(5) N(1)-C(5)-C(1) 110.1(4) N(1)-C(5)-C(6) 132.3(5) C(1)-C(5)-C(6) 117.5(5) N(2)-C(6)-C(5) 114.2(4) C(12)-C(7)-C(8) 120.2(5) C(12)-C(7)-N(2) 120.8(4) C(8)-C(7)-N(2) 118.8(4) C(7)-C(8)-C(9) 120.4(4) C(8)-C(9)-C(10) 118.1(5) C(8)-C(9)-C(13) 120.8(4) C(10)-C(9)-C(13) 121.0(5) C(11)-C(10)-C(9) 122.4(5) C(10)-C(11)-C(12) 118.7(4) C(10)-C(11)-C(14) 121.3(4) C(12)-C(11)-C(14) 119.9(5) C(7)-C(12)-C(11) 120.3(5) C(19)-C(15)-C(16) 107.6(4) C(19)-C(15)-C(20) 127.1(5) C(16)-C(15)-C(20) 125.2(5) C(19)-C(15)-Ir(1) 71.4(3) C(16)-C(15)-Ir(1) 66.8(3) C(20)-C(15)-Ir(1) 130.7(4) C(17)-C(16)-C(15) 107.7(4) C(17)-C(16)-C(21) 126.6(5) C(15)-C(16)-C(21) 124.9(5) C(17)-C(16)-Ir(1) 70.2(3) C(15)-C(16)-Ir(1) 74.7(3) C(21)-C(16)-Ir(1) 128.3(4) C(18)-C(17)-C(16) 108.0(4) C(18)-C(17)-C(22) 125.7(5) C(16)-C(17)-C(22) 126.3(5) C(18)-C(17)-Ir(1) 70.6(2) C(16)-C(17)-Ir(1) 70.6(3) C(22)-C(17)-Ir(1) 125.6(4) C(17)-C(18)-C(19) 107.1(4) C(17)-C(18)-C(23) 126.0(5) C(19)-C(18)-C(23) 126.2(5) S26

27 C(17)-C(18)-Ir(1) 70.3(3) C(19)-C(18)-Ir(1) 74.5(3) C(23)-C(18)-Ir(1) 127.9(4) C(15)-C(19)-C(18) 109.4(4) C(15)-C(19)-C(24) 126.2(5) C(18)-C(19)-C(24) 124.4(4) C(15)-C(19)-Ir(1) 72.2(3) C(18)-C(19)-Ir(1) 67.1(3) C(24)-C(19)-Ir(1) 124.9(3) Symmetry transformations used to generate equivalent atoms: S27

28 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Ir(1) 21(1) 20(1) 21(1) 0(1) 6(1) 2(1) Cl(1) 31(1) 25(1) 34(1) -7(1) 10(1) 1(1) N(1) 23(2) 46(3) 39(3) -8(2) 11(2) -3(2) N(2) 26(2) 22(2) 23(2) -3(2) 8(2) 0(2) C(1) 28(3) 24(2) 25(2) -6(2) 10(2) 3(2) C(2) 35(3) 36(3) 33(3) -2(2) 8(2) 8(2) C(3) 24(3) 56(4) 44(3) -17(3) 8(3) 3(3) C(4) 37(4) 90(5) 62(4) -11(4) 30(3) -14(3) C(5) 24(3) 33(3) 34(3) -4(2) 13(2) -1(2) C(6) 33(3) 26(3) 27(3) -2(2) 14(2) -6(2) C(7) 26(3) 29(3) 23(2) 3(2) 10(2) 5(2) C(8) 32(3) 21(2) 28(2) -1(2) 11(2) 0(2) C(9) 28(3) 28(3) 27(3) -2(2) 9(2) 1(2) C(10) 33(3) 31(3) 26(2) 3(2) 5(2) 6(2) C(11) 35(3) 26(3) 23(2) 5(2) 13(2) 4(2) C(12) 31(3) 25(2) 27(2) -1(2) 12(2) -4(2) C(13) 29(3) 33(3) 39(3) -3(2) 2(2) -1(2) C(14) 42(3) 28(3) 41(3) 3(2) 13(3) 3(2) C(15) 27(3) 31(3) 29(3) 1(2) 11(2) 8(2) C(16) 34(3) 23(2) 33(3) 1(2) 20(2) 5(2) C(17) 31(3) 28(3) 25(2) -8(2) 12(2) 2(2) C(18) 30(3) 31(3) 25(2) 3(2) 14(2) 4(2) C(19) 31(3) 26(3) 32(3) 1(2) 17(2) 4(2) C(20) 32(3) 47(3) 40(3) 6(2) 14(3) 12(2) C(21) 52(4) 27(3) 50(3) -6(2) 27(3) 4(3) C(22) 42(4) 48(4) 32(3) -10(2) 9(3) 2(3) C(23) 53(4) 38(3) 37(3) 15(2) 21(3) 15(3) C(24) 40(3) 36(3) 47(3) -4(2) 19(3) -10(2) S28

29 Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for x y z U(eq) H(2) H(3) H(4A) H(4B) H(4C) H(6) H(8) H(10) H(12) H(13A) H(13B) H(13C) H(14A) H(14B) H(14C) H(20A) H(20B) H(20C) H(21A) H(21B) H(21C) H(22A) H(22B) H(22C) H(23A) H(23B) H(23C) H(24A) H(24B) H(24C) S29