Ir(III)-Catalyzed Carbocarbation of Alkynes through Undirected Double C-H Bond Activation of Anisoles.
Romanov-Michailidis, Fedor; Ravetz, Benjamin D.; Paley, Daniel W.; Rovis, Tomislav; Journal of the American Chemical Society 140 (2018) 5370–5374; doi:10.1021/jacs.8b02716

data_4132276
_publ_section_title
;
 Ir(III)-Catalyzed Carbocarbation of Alkynes through Undirected Double C-H
 Bond Activation of Anisoles.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5370
_journal_page_last               5374
_journal_paper_doi               10.1021/jacs.8b02716
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         '1(C44 H34 Cl4 F12 Ir2)'
_chemical_formula_sum            'C44 H34 Cl4 F12 Ir2'
_chemical_formula_weight         1316.91
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-08-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-08-22 deposited with the CCDC.
2017-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                91.4050(10)
_cell_angle_beta                 108.247(2)
_cell_angle_gamma                107.063(2)
_cell_formula_units_Z            4
_cell_length_a                   13.5428(3)
_cell_length_b                   18.8283(3)
_cell_length_c                   18.9337(3)
_cell_measurement_reflns_used    34008
_cell_measurement_temperature    99.9(3)
_cell_measurement_theta_max      72.7550
_cell_measurement_theta_min      3.6870
_cell_volume                     4347.10(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     11.00  37.00   0.50    0.50    --   37.78 -99.00  60.00   52
  2  \w     45.00  71.00   0.50    0.50    --   37.78 -99.00  60.00   52
  3  \w     46.00  76.00   0.50    0.50    --   37.78 -99.00 -30.00   60
  4  \w     91.00 116.00   0.50    1.00    --  111.00-111.00-120.00   50
  5  \w     92.00 137.00   0.50    1.00    --  111.00 -77.00-150.00   90
  6  \w     90.00 128.00   0.50    1.00    --  111.00 -61.00-150.00   76
  7  \w     84.00 129.00   0.50    1.00    --  111.00 -61.00 -60.00   90
  8  \w     90.00 115.00   0.50    1.00    --  111.00-111.00 -60.00   50
  9  \w     74.00 114.00   0.50    1.00    --  111.00-111.00   0.00   80
 10  \w     86.00 112.00   0.50    1.00    --  111.00-111.00  60.00   52
 11  \w     76.00 108.00   0.50    1.00    --  111.00 -94.00  30.00   64
 12  \w     91.00 128.00   0.50    1.00    --  111.00 -45.00  30.00   74
 13  \w     87.00 128.00   0.50    1.00    --  111.00 -15.00 -30.00   82
 14  \w     79.00 108.00   0.50    1.00    --  111.00 -45.00 -60.00   58
 15  \w     64.00  90.00   0.50    1.00    --  111.00 -94.00-120.00   52
 16  \w     75.00 109.00   0.50    1.00    --  111.00 -94.00-150.00   68
 17  \w     64.00  91.00   0.50    1.00    --  111.00 -94.00-180.00   54
 18  \w     62.00 113.00   0.50    1.00    --  111.00-111.00-180.00  102
 19  \w     56.00  84.00   0.50    1.00    --  111.00 -30.00-150.00   56
 20  \w     62.00 103.00   0.50    1.00    --  111.00 -30.00-120.00   82
 21  \w     57.00  83.00   0.50    1.00    --  111.00 -61.00-150.00   52
 22  \w     49.00 148.00   0.50    1.00    --  111.00 -15.00 -90.00  198
 23  \w     94.00 141.00   0.50    1.00    --  111.00  45.00-150.00   94
 24  \w    125.00 150.00   0.50    1.00    --  111.00 111.00 -60.00   50
 25  \w    116.00 145.00   0.50    1.00    --  111.00 111.00   0.00   58
 26  \w    119.00 145.00   0.50    1.00    --  111.00  77.00  90.00   52
 27  \w     91.00 160.00   0.50    1.00    --  111.00  30.00 150.00  138
 28  \w     61.00 110.00   0.50    1.00    --  111.00 -45.00 150.00   98
 29  \w     60.00 114.00   0.50    1.00    --  111.00-111.00 120.00  108
 30  \w     55.00  84.00   0.50    1.00    --  111.00-111.00  90.00   58
 31  \w     49.00  75.00   0.50    1.00    --  111.00 -94.00  90.00   52
 32  \w     47.00 106.00   0.50    1.00    --  111.00 -77.00  90.00  118
 33  \w     66.00 111.00   0.50    1.00    --  111.00 -20.00  79.92   90
 34  \w     66.00  91.00   0.50    1.00    --  111.00 -61.00 -30.00   50
 35  \w     50.00  75.00   0.50    1.00    --  111.00 -61.00 -60.00   50
 36  \w     49.00  77.00   0.50    1.00    --  111.00 -45.00-120.00   56
 37  \w     44.00  73.00   0.50    1.00    --  111.00 -45.00-150.00   58
 38  \w     46.00 135.00   0.50    1.00    --  111.00 -15.00-180.00  178
 39  \w     47.00  95.00   0.50    1.00    --  111.00 -30.00  30.00   96
 40  \w     45.00  90.00   0.50    1.00    --  111.00 -77.00 -30.00   90
 41  \w     42.00  81.00   0.50    1.00    --  111.00-111.00-120.00   78
 42  \w     42.00  74.00   0.50    1.00    --  111.00 -30.00   0.00   64
 43  \w     42.00  67.00   0.50    1.00    --  111.00 -94.00  30.00   50
 44  \w     43.00  79.00   0.50    1.00    --  111.00-111.00  60.00   72
 45  \w     45.00  93.00   0.50    1.00    --  111.00 -61.00 150.00   96
 46  \w    -57.00  31.00   0.50    0.50    --  -37.78  37.00 150.00  176
 47  \w    -61.00 -35.00   0.50    0.50    --  -37.78 178.00  90.00   52
 48  \w   -102.00 -75.00   0.50    0.50    --  -37.78 178.00  90.00   54
 49  \w     67.00 109.00   0.50    0.50    --   37.78 178.00-180.00   84
 50  \w     84.00 109.00   0.50    0.50    --   37.78 178.00 -30.00   50
 51  \w     64.00 109.00   0.50    1.00    --  111.00 178.00  90.00   90
 52  \w     64.00  94.00   0.50    1.00    --  111.00 178.00  30.00   60
 53  \w   -105.00 -32.00   0.50    0.50    --  -37.78 -37.00-150.00  146
 54  \w     19.00  76.00   0.50    0.50    --   37.78 -99.00-180.00  114
 55  \w   -106.00 -25.00   0.50    0.50    --  -37.78 -37.00 -30.00  162
 56  \w   -102.00 -41.00   0.50    0.50    --  -37.78-178.00-150.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0350461000
_diffrn_orient_matrix_UB_12      0.0485877000
_diffrn_orient_matrix_UB_13      0.0480273000
_diffrn_orient_matrix_UB_21      0.1213101000
_diffrn_orient_matrix_UB_22      0.0413019000
_diffrn_orient_matrix_UB_23      0.0451979000
_diffrn_orient_matrix_UB_31      0.0025644000
_diffrn_orient_matrix_UB_32      0.0581490000
_diffrn_orient_matrix_UB_33      -0.0557965000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.029
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18944
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.994
_diffrn_reflns_theta_min         3.624
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.696
_exptl_absorpt_correction_T_max  0.789
_exptl_absorpt_correction_T_min  0.217
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.012
_exptl_crystal_description       block
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.036
_refine_diff_density_max         2.915
_refine_diff_density_min         -2.181
_refine_diff_density_rms         0.183
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1221
_refine_ls_number_reflns         18944
_refine_ls_number_restraints     259
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0632P)^2^+24.1691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1083
_refine_ls_wR_factor_ref         0.1094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17885
_reflns_number_total             18944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02716_si_004.cif
_cod_data_source_block           Cldimer
_cod_original_cell_volume        4347.10(15)
_cod_database_code               4132276
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'Ir2 Cl4 C44 H34 F12'
_olex2_refinement_description
;
1. Shared sites
{H71B, H71}
2. Others
 Fixed Uiso: H7A(0.038) H7B(0.038) H7C(0.038) H8A(0.038) H8B(0.038) H8C(0.038)
 H9A(0.034) H9B(0.034) H9C(0.034) H11(0.034) H12(0.042) H14(0.04) H15(0.037)
 H21(0.031) H22(0.033) H24(0.037) H25(0.034) H57A(0.038) H57B(0.038)
 H57C(0.038) H58A(0.038) H58B(0.038) H58C(0.038) H59A(0.039) H59B(0.039)
 H59C(0.039) H61(0.052) H62(0.05) H64(0.041) H65(0.039) H71(0.041) H72(0.05)
 H74(0.033) H75(0.028) H71B(0.041) H72B(0.046) H74B(0.033) H75B(0.025)
 H10A(0.037) H10B(0.037) H10C(0.037) H10D(0.039) H10E(0.039) H10F(0.039)
 H10G(0.037) H10H(0.037) H10I(0.037) H111(0.05) H112(0.058) H114(0.061)
 H115(0.047) H121(0.034) H122(0.037) H124(0.038) H125(0.033) H15A(0.036)
 H15B(0.036) H15C(0.036) H15D(0.036) H15E(0.036) H15F(0.036) H15G(0.039)
 H15H(0.039) H15I(0.039) H161(0.033) H162(0.038) H164(0.039) H165(0.037)
 H171(0.05) H172(0.059) H174(0.038) H175(0.031)
 Fixed X: H7A(0.156128) H7B(0.037843) H7C(0.113202) H8A(0.030435)
 H8B(0.149178) H8C(0.058395) H9A(-0.191006) H9B(-0.23075) H9C(-0.160207)
 H11(0.241913) H12(0.428646) H14(0.458471) H15(0.269692) H21(-0.198929) H22(-
 0.351852) H24(-0.303343) H25(-0.152786) H57A(-0.153107) H57B(-0.074948) H57C(-
 0.032723) H58A(0.150661) H58B(0.227728) H58C(0.179758) H59A(-0.086998) H59B(-
 0.161103) H59C(-0.042178) H61(0.136489) H62(0.287131) H64(0.384418)
 H65(0.233262) H71(-0.286893) H72(-0.472181) H74(-0.397713) H75(-0.213395)
 H71B(-0.29683) H72B(-0.478572) H74B(-0.380398) H75B(-0.199512) H10A(-0.871822)
 H10B(-0.950128) H10C(-0.829174) H10D(-0.876607) H10E(-0.811362) H10F(-
 0.932048) H10G(-1.120236) H10H(-1.196111) H10I(-1.147578) H111(-0.699326)
 H112(-0.510354) H114(-0.540748) H115(-0.731031) H121(-1.169387) H122(-
 1.327768) H124(-1.304605) H125(-1.143172) H15A(-1.145031) H15B(-1.028443)
 H15C(-1.082308) H15D(-0.772985) H15E(-0.738506) H15F(-0.804827) H15G(-
 0.978318) H15H(-1.102796) H15I(-1.044433) H161(-0.746236) H162(-0.60251) H164(-
 0.718361) H165(-0.859995) H171(-1.252231) H172(-1.436755) H174(-1.376078)
 H175(-1.191258)
 Fixed Y: H7A(0.118435) H7B(0.075463) H7C(0.030635) H8A(0.133168)
 H8B(0.132505) H8C(0.058028) H9A(-0.001996) H9B(0.05184) H9C(0.083274)
 H11(0.018049) H12(0.051069) H14(0.262971) H15(0.229539) H21(-0.081188) H22(-
 0.135324) H24(0.060541) H25(0.115418) H57A(0.397569) H57B(0.480032)
 H57C(0.412652) H58A(0.414652) H58B(0.451644) H58C(0.500816) H59A(0.447834)
 H59B(0.367439) H59C(0.379751) H61(0.568653) H62(0.619805) H64(0.440544)
 H65(0.389716) H71(0.283513) H72(0.271099) H74(0.49552) H75(0.506616)
 H71B(0.291959) H72B(0.288968) H74B(0.511419) H75B(0.513374) H10A(0.086515)
 H10B(0.04743) H10C(0.096573) H10D(0.387698) H10E(0.38431) H10F(0.386386)
 H10G(0.30428) H10H(0.223937) H10I(0.283869) H111(0.245077) H112(0.288901)
 H114(0.32178) H115(0.276885) H121(0.112197) H122(0.010509) H124(-0.041557)
 H125(0.055613) H15A(0.385018) H15B(0.445277) H15C(0.406008) H15D(0.242436)
 H15E(0.296867) H15F(0.212203) H15G(0.12394) H15H(0.117644) H15I(0.114928)
 H161(0.422728) H162(0.531564) H164(0.546378) H165(0.437863) H171(0.195938)
 H172(0.141428) H174(0.198629) H175(0.249576)
 Fixed Z: H7A(0.095679) H7B(0.040729) H7C(0.084829) H8A(0.366227)
 H8B(0.375063) H8C(0.374515) H9A(0.25275) H9B(0.196728) H9C(0.280617)
 H11(0.282586) H12(0.337278) H14(0.295215) H15(0.240215) H21(0.10604) H22(-
 0.000188) H24(-0.08424) H25(0.022022) H57A(0.386051) H57B(0.414327)
 H57C(0.440228) H58A(0.191644) H58B(0.272922) H58C(0.214452) H59A(0.105744)
 H59B(0.109223) H59C(0.107761) H61(0.422386) H62(0.528245) H64(0.510832)
 H65(0.404416) H71(0.20788) H72(0.165455) H74(0.203918) H75(0.241046)
 H71B(0.198639) H72B(0.160253) H74B(0.224586) H75B(0.260962) H10A(-0.476669)
 H10B(-0.433296) H10C(-0.38877) H10D(-0.452151) H10E(-0.368446) H10F(-0.390663)
 H10G(-0.4228) H10H(-0.462501) H10I(-0.509032) H111(-0.278452) H112(-0.247071)
 H114(-0.458415) H115(-0.493307) H121(-0.59053) H122(-0.639732) H124(-0.432905)
 H125(-0.384086) H15A(-0.118553) H15B(-0.08907) H15C(-0.032101) H15D(-0.00419)
 H15E(-0.059815) H15F(-0.088848) H15G(-0.123618) H15H(-0.153015) H15I(-0.06784)
 H161(-0.112115) H162(-0.058179) H164(0.111723) H165(0.057943) H171(-0.2292)
 H172(-0.245528) H174(-0.027878) H175(-0.010213)
;
_shelx_res_checksum              82817
_shelx_hkl_checksum              12343
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.711
_oxdiff_exptl_absorpt_empirical_full_min 0.729
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -179.8477\% 
 around [-0.00 -0.71 0.71] (reciprocal) or [0.02 -0.71 0.71] (direct)
;