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

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

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). 3 6-31G** 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, 2004. 2. Andrae, D.; Häusserman, U.; Dolg, M.; Stoll, H.; Preuss, Η. Theor. Chim. Acta 1990, 77, 123. 3. 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, 237. 4. (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257. (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213. S2

3 Energy = -830.021590 Enthalpy (0K) = -829.783554 Enthalpy (298.15 K) = -829.765605 Free Energy = -829.831562 C -3.736620-0.308899-1.440552 N -2.586098-0.060860-0.749786 C -2.805515-0.297788 0.608183 C -4.146595-0.736704 0.739755 C -4.718939-0.759880-0.544820 Ir 0.872363-0.110425 0.086522 N -0.557680 0.054619 1.590287 C -1.863916-0.138323 1.657155 C 0.797719-2.143442-0.698398 C 1.580065-1.319770-1.608372 C 2.721728-0.806217-0.910605 C 2.658037-1.310213 0.458727 C 1.494175-2.148772 0.574407 O -0.174513 1.501053-0.903309 H -0.132955 0.201496 2.510680 H -2.300502-0.183245 2.665826 H -4.620890-1.029367 1.676537 H -5.731535-1.058625-0.809514 H -3.793984-0.133391-2.514136 H 3.488967-0.148682-1.318474 H 3.369267-1.088122 1.254949 H 1.164859-2.659771 1.479740 H -0.109444-2.694308-0.943092 H 1.311012-1.086883-2.639930 C 0.421703 2.402344-0.177415 C 0.098683 3.856893-0.293996 H -0.822775 4.074285 0.274081 H 0.917393 4.462211 0.119678 H -0.083195 4.122773-1.346353 O 1.293501 1.945722 0.648916 H -1.776796 0.458454-1.104946 S3

TS 3-5 Energy = -829.992930184 Enthalpy (0K) = -829.756845 Enthalpy (298.15 K) = -829.739639 Free Energy = -829.802827 Nimag = 1 (-123.4 cm -1 ) C -2.832166 0.150655-1.513250 N -1.896391 0.460612-0.543850 C -2.512687 0.242424 0.714776 C -3.819683-0.219954 0.498896 C -4.009700-0.295167-0.907337 Ir 0.602063-0.325226 0.116762 N -0.412930 0.311477 1.817718 C -1.726294 0.373536 1.892998 C 0.146201-2.292170-0.766920 C 1.116838-1.589052-1.617886 C 2.287436-1.342292-0.847916 C 2.047289-1.830006 0.510307 C 0.729120-2.475296 0.522328 O -0.263255 2.497756-0.798332 H 0.107805 0.540682 2.668789 H -2.212292 0.533179 2.865987 H -4.530172-0.512608 1.272715 H -4.914524-0.611845-1.424517 H -2.619428 0.341691-2.565105 H 3.171980-0.795559-1.174419 H 2.759481-1.799731 1.336189 H 0.259563-2.956269 1.379800 H -0.855515-2.597759-1.067156 H 0.956625-1.292466-2.655097 C 0.888634 2.556394-0.298453 C 1.640194 3.869861-0.232452 H 1.048303 4.587777 0.360578 H 2.636087 3.752034 0.212569 H 1.726918 4.284193-1.247994 O 1.540086 1.520277 0.187253 H -1.204300 1.298033-0.682408 S4

5 Energy = -830.021405043 Enthalpy (0K) = -829.784016 Enthalpy (298.15 K) = -829.766303 Free Energy = -829.829970 C -2.029529-1.506959-1.054351 N -1.326213-0.780062-0.123593 C -2.066393-0.825819 1.076363 C -3.256910-1.552293 0.858420 C -3.229137-1.978148-0.484614 Ir 0.646928-0.098511 0.083572 N -0.190098 0.228295 1.962352 C -1.420834-0.213024 2.173781 C 1.629879-1.590489-1.193983 C 2.150826-0.302682-1.540703 C 2.798298 0.253129-0.352201 C 2.663527-0.698499 0.708113 C 1.907138-1.844944 0.213511 O 0.092388 1.988408-0.299071 C -0.992732 2.483203-0.713607 C -1.117273 3.956738-0.968371 O -2.076520 1.773599-0.955224 H -1.663188-1.619754-2.075007 H -4.039589-1.741423 1.592844 H -3.992673-2.556170-1.003933 H 0.287136 0.701875 2.731580 H -1.893858-0.106691 3.157161 H 1.071761-2.253253-1.856330 H 2.082012 0.177911-2.516374 H 3.282036 1.227558-0.284642 H 3.028987-0.572180 1.728083 H 1.675054-2.756236 0.763747 H -1.920730 4.370784-0.336852 H -0.169309 4.465585-0.755250 H -1.412470 4.124155-2.017429 H -1.882558 0.808229-0.733786 S5

4 Energy = -830.017180327 Enthalpy (0K) = -829.779482 Enthalpy (298.15 K) = -829.761360 Free Energy = -829.827594 C -3.524968-0.478567-2.219929 C -2.409370-0.252897-1.392309 C -2.755969-0.648466-0.078152 N -4.082140-1.095366-0.138236 C -4.545975-1.009357-1.415096 Ir 0.844985-0.040847 0.178278 N -0.805702-0.361289 1.396420 C -2.077724-0.618547 1.171997 C 0.927265-1.849292-1.048488 C 1.529144-0.756569-1.775539 C 2.675551-0.270987-1.039305 C 2.772449-1.073638 0.163778 C 1.709226-2.048232 0.164078 O -0.043446 1.883446-0.247686 H -0.569657-0.339174 2.393453 H -2.693097-0.834923 2.060142 H -4.611488-1.468269 0.647334 H -5.557400-1.320811-1.670944 H -3.606147-0.267280-3.284788 H 3.343150 0.537047-1.335041 H 3.500702-0.932240 0.963978 H 1.527443-2.796663 0.934998 H 0.054268-2.422579-1.357586 H 1.154430-0.335677-2.709955 C 0.423350 2.390712 0.845424 C 0.132680 3.797325 1.262840 H -0.761697 3.810877 1.909895 H 0.977036 4.203960 1.838604 H -0.070040 4.421368 0.380574 O 1.142440 1.590712 1.564080 H -1.462319 0.204018-1.672288 S6

TS 4-6 Energy = -829.982648090 Enthalpy (0K) = -829.746618 Enthalpy (298.15 K) = -829.729097 Free Energy = -829.793339 Nimag = 1 (-116.952 cm -1 ) C -2.726511-0.276869-1.877090 C -1.927743 0.003920-0.736023 C -2.492786-0.712897 0.351537 N -3.611278-1.374267-0.121307 C -3.755328-1.128890-1.465607 Ir 0.583326-0.169901 0.148553 N -0.655452-0.492334 1.780684 C -1.933637-0.773610 1.662738 C 0.943014-1.831799-1.279903 C 1.518349-0.589369-1.809250 C 2.512504-0.121631-0.902255 C 2.527608-1.022245 0.249651 C 1.576928-2.105025-0.029238 O -0.145462 2.524823-0.700407 H -0.299925-0.343021 2.730809 H -2.534480-1.007170 2.552513 H -4.193069-2.014482 0.416588 H -4.587171-1.554014-2.025169 H -2.623233 0.157675-2.870001 H 3.091115 0.796956-1.000202 H 3.187889-0.948529 1.114316 H 1.363616-2.946164 0.631459 H 0.165712-2.428284-1.755734 H 1.211605-0.087549-2.727282 C 0.411182 2.678494 0.405475 C 0.649823 4.043088 1.022331 H -0.324242 4.520384 1.219002 H 1.225257 3.982710 1.955795 H 1.179886 4.677001 0.293864 O 0.835482 1.658830 1.140446 H -1.252492 0.894809-0.664665 S7

6 Energy = -830.01494992 Enthalpy (0K) = -829.777539 Enthalpy (298.15 K) = -829.759630 Free Energy = -829.823687 C -2.058195-1.484574-1.149249 C -1.253283-0.862278-0.148902 C -2.039307-0.876295 1.038440 N -3.257860-1.481425 0.768507 C -3.277380-1.850759-0.549646 Ir 0.628108-0.095382 0.114495 N -0.213668 0.087876 2.031142 C -1.461732-0.320466 2.203835 C 1.599437-1.646012-1.051503 C 2.004470-0.378106-1.603020 C 2.803663 0.303493-0.584078 C 2.849562-0.500758 0.578992 C 2.058720-1.707726 0.323850 O 0.051579 1.988849-0.069248 C -0.909466 2.475690-0.726884 C -1.059574 3.961305-0.878495 O -1.834415 1.750441-1.323594 H -1.810269-1.662563-2.195796 H -4.015346-1.643745 1.428876 H -4.144559-2.353199-0.976611 H 0.240752 0.558372 2.816584 H -1.964502-0.211939 3.172856 H 1.017229-2.413522-1.561470 H 1.830629-0.031217-2.620810 H 3.233760 1.300920-0.684773 H 3.348350-0.250690 1.515410 H 1.931167-2.549296 1.004292 H -2.034900 4.277121-0.473196 H -0.246530 4.482748-0.358800 H -1.054851 4.222547-1.949779 H -1.673375 0.778347-1.107776 S8

[IrCl(Cp)(κ N,N NH=CH-NC 4 H 3 )] Energy = -616.186152771 Enthalpy (0K) = -616.010317 Enthalpy (298.15 K) = -615.996319 Free Energy = -616.051178 C 1.280870-1.478639-1.367631 C 1.656346-0.164221-1.850132 C 2.495275 0.435356-0.824524 C 2.642530-0.489875 0.259697 C 1.880159-1.690834-0.070640 Ir 0.493523 0.018520 0.017016 N -1.525175-0.331572-0.244823 C -2.298244-0.393823 0.919381 C -3.656326-0.594937 0.563860 C -3.690983-0.640706-0.838376 C -2.358749-0.467819-1.300785 Cl -0.060333 2.372796 0.096373 N -0.251012-0.034743 1.957513 C -1.559382-0.188882 2.101484 H 0.289380 0.238739 2.778347 H -2.024588-0.140234 3.093308 H -4.496936-0.683202 1.252072 H -4.566827-0.786621-1.470847 H -1.987761-0.429999-2.324981 H 2.884491 1.453398-0.845692 H 3.212870-0.319114 1.172325 H 1.791122-2.589920 0.538349 H 0.627141-2.183306-1.883247 H 1.379797 0.287135-2.801065 S9

[IrCl(Cp)(κ N,C NH=CH-NC 4 H 3 )] Energy = -616.171560107 Enthalpy (0K) = -615.995824 Enthalpy (298.15 K) = -615.981515 Free Energy = -616.036764 C 1.267147-1.432153-1.379906 C 1.669997-0.118806-1.837404 C 2.594090 0.412186-0.841141 C 2.751574-0.529584 0.205773 C 1.887508-1.668989-0.091598 Ir 0.485447 0.024190 0.023528 C -1.474398-0.333341-0.305583 C -2.268896-0.382821 0.871462 N -3.595410-0.609230 0.518898 C -3.659995-0.696527-0.852825 C -2.376080-0.531941-1.389690 Cl -0.005346 2.389710 0.159585 N -0.287516-0.045173 1.961319 C -1.603545-0.166491 2.094716 H 0.236258 0.262484 2.782229 H -2.084551-0.076591 3.076879 H -4.390118-0.669946 1.147648 H -4.613227-0.873860-1.350700 H -2.144837-0.538597-2.454659 H 3.020631 1.415480-0.861391 H 3.354615-0.398690 1.103735 H 1.790579-2.575125 0.506320 H 0.601176-2.119324-1.901985 H 1.397045 0.358074-2.777036 S10

4-membered C-H activation TS ( σ-bond metathesis ) Energy = -829.965158 Enthalpy (0K) = -829.733668 Enthalpy (298.15 K) = -829.716111 Free Energy = -829.778986 Nimag = 1 (-949.41 cm -1 ) C -1.056915-1.767558 1.421412 C -1.857224-0.566382 1.525966 C -2.631068-0.457135 0.300937 C -2.296775-1.546835-0.559771 C -1.295260-2.361551 0.126094 Ir -0.426136-0.386389-0.143139 C 1.570591 0.071671 0.517779 C 2.521021-0.306006-0.478281 N 3.769216-0.330744 0.084537 C 3.672075 0.015525 1.419316 C 2.332492 0.262391 1.720936 O -0.030645 1.737043-0.612898 N 0.734773-0.661390-1.876127 C 2.046223-0.612007-1.792956 H 0.338732-0.784252-2.812425 H 2.686286-0.768988-2.669958 H 4.641680-0.567931-0.387453 H 4.561414 0.062204 2.046165 H 1.960454 0.586224 2.692511 H -3.296030 0.371414 0.060576 H -2.708471-1.732497-1.551533 H -0.844118-3.279875-0.249775 H -0.362376-2.144240 2.172682 H -1.913258 0.113005 2.373885 C -0.833148 2.694489-0.025709 O -1.813023 2.414445 0.647223 C -0.371217 4.097587-0.361251 H -1.015165 4.828799 0.144305 H 0.678138 4.241286-0.055795 H -0.415082 4.252253-1.451957 H 0.916936 1.162433 0.090211 S11

4-membered N-H activation TS ( σ-bond metathesis ) Energy = -829.981890 Enthalpy (0K) = -829.749786 Enthalpy (298.15 K) = -829.732377 Free Energy = -829.795387 Nimag = 1 (-983.52 cm -1 ) C 1.719038-1.819534-0.911055 C 2.218333-0.565048-1.395510 C 2.710084 0.187398-0.244809 C 2.520243-0.622926 0.928327 C 1.882225-1.868574 0.533990 Ir 0.577250-0.199129 0.040427 N -1.531022-0.586699-0.446431 C -2.317916-0.654784 0.741809 C -3.439390-1.444577 0.503935 C -3.346810-1.910920-0.845308 C -2.182776-1.394428-1.391593 O -0.424721 1.494420-0.873651 N -0.468386 0.330471 1.759826 C -1.731034-0.019778 1.876354 H -0.048038 0.874943 2.517077 H -2.292587 0.172782 2.798552 H -4.230386-1.675883 1.217982 H -4.069322-2.543626-1.360146 H -1.790409-1.481371-2.404457 H 3.127625 1.193994-0.264273 H 2.774877-0.329776 1.947712 H 1.630994-2.705310 1.184660 H 1.249656-2.595255-1.517663 H 2.216755-0.225358-2.430772 C -0.404238 2.743242-0.261292 O 0.366432 2.985198 0.651094 C -1.365885 3.718773-0.900250 H -1.367497 4.658721-0.333137 H -1.055435 3.915996-1.940052 H -2.384367 3.298459-0.940211 H -1.319181 0.638183-0.809042 S12

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 9 10 8 7 Me 11 N Ir 12 Cl 1 6 2 N 5 3 4 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, 5.00. 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 ), 21.45 (2x Me), 86.30 (C 5 Me 5 ), 113.72 (C 4 ), 118.02 (C 3 ), 121.45 (C 8, C 12 ), 128.07 (C 10 ), 135.35 (C 5 ), 138.55 (C 9, C 11 ), 142.25 (C 2 ), 151.43 (C 7 ), 157.97 (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 9 10 8 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, 4.88. 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 ), 21.49 (2x Me), 34.87 (NMe) 86.25 (C 5 Me 5 ), 112.85 (C 5 ), 120.56 (C 8, C 12 ), 127.36 (C 10 ), 131.51 (C 4 ), 138.33 (C 9, C 11 ), 145.105 (C 2 ), 152.54 (C 7 ), 155.92 (C 6 ), 157.09 (C 1 ). MS (FAB): m/z 574 [M] +, 539 [M-Cl] +. ν(c=n) 1610 cm -1. 11 Ir 12 Cl 1 N 5 4 S13

Table 1. Crystal data and structure refinement for 1a (ID code 03008). Identification code 03008 Empirical formula C23 H28 Cl Ir N2 Formula weight 560.12 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 16.480(8) Å α= 90. b = 8.143(4) Å β= 111.954(7). c = 16.836(8) Å γ = 90. Volume 2095.6(17) Å 3 Z 4 Density (calculated) 1.775 Mg/m 3 Absorption coefficient 6.509 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 26.00. Index ranges -20<=h<=20, -10<=k<=10, -20<=l<=20 Reflections collected 14381 Independent reflections 4110 [R(int) = 0.0686] Completeness to theta = 26.00 100.0 % 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 2 1.026 Final R indices [I>2sigma(I)] R1 = 0.0296, wr2 = 0.0659 R indices (all data) R1 = 0.0321, wr2 = 0.0670 Largest diff. peak and hole 1.235 and -1.294 e.å -3 S14

Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 03008. 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

Table 3. Bond lengths [Å] and angles [ ] for 03008. 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) 2.3950(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

N(1)-Ir(1)-C(14) 119.71(14) N(2)-Ir(1)-C(14) 100.82(13) N(1)-Ir(1)-C(16) 107.49(14) N(2)-Ir(1)-C(16) 166.71(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) 128.21(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) 144.21(14) N(2)-Ir(1)-C(17) 139.35(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) 158.91(14) N(2)-Ir(1)-C(18) 106.84(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) 154.30(12) C(16)-Ir(1)-Cl(1) 106.56(11) C(15)-Ir(1)-Cl(1) 145.12(11) C(17)-Ir(1)-Cl(1) 93.45(11) C(18)-Ir(1)-Cl(1) 114.91(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

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

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

Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for 03008. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U 11 +... + 2 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

Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 03008. x y z U(eq) H(1) 8099 1547 8075 35 H(2) 9540 2590 9081 40 H(3) 10079 4609 8285 38 H(5) 9211 5732 6473 26 H(7) 9184 5339 5070 27 H(9) 7604 7913 3064 31 H(11) 6678 6126 4783 29 H(12A) 9733 7437 4154 49 H(12B) 9058 7567 3208 49 H(12C) 9441 5852 3589 49 H(13A) 6143 8444 2852 52 H(13B) 5968 8629 3701 52 H(13C) 5687 7020 3155 52 H(19A) 8366 448 5005 82 H(19B) 8051 2164 4580 82 H(19C) 7613 554 4100 82 H(20A) 8363-948 6143 63 H(20B) 7640-1901 6351 63 H(20C) 8145-450 6941 63 H(21A) 5901 1044 6854 56 H(21B) 6712-137 7149 56 H(21C) 5816-732 6471 56 H(22A) 4899 3307 4709 58 H(22B) 5144 3166 5700 58 H(22C) 4666 1710 5098 58 H(23A) 5762 2106 3421 74 H(23B) 6518 3403 3746 74 H(23C) 5629 3732 3856 74 S21

Table 1. Crystal data and structure refinement for 2 (ID code 03069). Identification code 03069 Empirical formula C24 H30 Cl Ir N2 Formula weight 574.15 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = 37.618(4) Å α= 90. b = 8.1812(9) Å β= 112.402(2). c = 15.3211(17) Å γ = 90. Volume 4359.4(8) Å 3 Z 8 Density (calculated) 1.750 Mg/m 3 Absorption coefficient 6.260 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 26.00. Index ranges -45<=h<=46, -10<=k<=10, -18<=l<=18 Reflections collected 16473 Independent reflections 4286 [R(int) = 0.0547] Completeness to theta = 26.00 99.8 % Absorption correction Empirical Max. and min. transmission 0.802 and 0.468 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4286 / 0 / 261 Goodness-of-fit on F 2 1.013 Final R indices [I>2sigma(I)] R1 = 0.0323, wr2 = 0.0741 R indices (all data) R1 = 0.0373, wr2 = 0.0762 Largest diff. peak and hole 1.609 and -1.879 e.å -3 S22

Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 03069. 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

Table 3. Bond lengths [Å] and angles [ ] for 03069. 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) 2.3940(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

C(1)-Ir(1)-N(2) 77.68(18) C(1)-Ir(1)-C(17) 96.32(19) N(2)-Ir(1)-C(17) 131.62(18) C(1)-Ir(1)-C(18) 110.46(19) N(2)-Ir(1)-C(18) 166.59(17) C(17)-Ir(1)-C(18) 39.07(19) C(1)-Ir(1)-C(16) 117.62(19) N(2)-Ir(1)-C(16) 101.38(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) 148.05(19) N(2)-Ir(1)-C(19) 134.27(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) 156.06(19) N(2)-Ir(1)-C(15) 104.28(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) 140.42(14) C(18)-Ir(1)-Cl(1) 102.80(13) C(16)-Ir(1)-Cl(1) 153.92(15) C(19)-Ir(1)-Cl(1) 92.75(12) C(15)-Ir(1)-Cl(1) 115.74(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

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

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

Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for 03069. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U 11 +... + 2 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

Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 03069. x y z U(eq) H(2) 91 4195-1406 43 H(3) -393 3312-758 51 H(4A) -403 1901 672 89 H(4B) -5 1997 1567 89 H(4C) -110 393 920 89 H(6) 741 1101 1772 34 H(8) 1684 3645 2185 33 H(10) 2365-53 3616 38 H(12) 1298-1012 1752 33 H(13A) 2342 4208 3119 55 H(13B) 2638 2725 3512 55 H(13C) 2402 3391 4115 55 H(14A) 2018-3052 2432 57 H(14B) 1673-3153 2798 57 H(14C) 2102-2786 3527 57 H(20A) 2145 1573 146 59 H(20B) 1944 1055 855 59 H(20C) 2111 2865 893 59 H(21A) 1017-752 -829 61 H(21B) 1421-652 46 61 H(21C) 1410-850 -1004 61 H(22A) 426 2621-2246 63 H(22B) 554 783-1916 63 H(22C) 666 1600-2725 63 H(23A) 982 5503-2476 62 H(23B) 1002 6508-1563 62 H(23C) 640 5361-2102 62 H(24A) 1634 6277 95 60 H(24B) 1748 6180-810 60 H(24C) 2006 5266 146 60 S29