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_4132275
_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         'C20 H29 Ir O2 S'
_chemical_formula_sum            'C20 H29 Ir O2 S'
_chemical_formula_weight         525.69
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2016-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.31 svn.r3340 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-08-22 deposited with the CCDC.
2017-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                80.224(2)
_cell_angle_beta                 89.855(2)
_cell_angle_gamma                87.327(2)
_cell_formula_units_Z            4
_cell_length_a                   8.2520(2)
_cell_length_b                   9.1752(2)
_cell_length_c                   26.1498(5)
_cell_measurement_reflns_used    17616
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.6310
_cell_measurement_theta_min      4.8890
_cell_volume                     1949.00(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -53.00  30.00   1.00    1.00    --  -36.45  57.00 -90.00   83
  2  \w    -63.00  16.00   1.00    1.00    --  -36.45  77.00  60.00   79
  3  \w    -26.00   7.00   1.00    1.00    --  -36.45  37.00 150.00   33
  4  \w    -52.00 -26.00   1.00    1.00    --  -36.45  57.00 150.00   26
  5  \w   -103.00 -52.00   1.00    1.00    --  -36.45 -57.00   0.00   51
  6  \w   -103.00 -47.00   1.00    1.00    --  -36.45 -77.00 -30.00   56
  7  \w   -100.00 -70.00   1.00    1.00    --  -36.45 -57.00-150.00   30
  8  \w     47.00  73.00   1.00    1.00    --   36.45 -99.00 120.00   26
  9  \w     18.00  75.00   1.00    1.00    --   36.45 -99.00 -30.00   57
 10  \w     48.00  74.00   1.00    1.00    --   36.45 -99.00-120.00   26
 11  \w     84.00 110.00   1.00    4.00    --  111.00-111.00   0.00   26
 12  \w     89.00 115.00   1.00    4.00    --  111.00-111.00  30.00   26
 13  \w     94.00 129.00   1.00    4.00    --  111.00 -77.00  60.00   35
 14  \w     92.00 118.00   1.00    4.00    --  111.00 -61.00  30.00   26
 15  \w     87.00 113.00   1.00    4.00    --  111.00 -77.00   0.00   26
 16  \w     89.00 115.00   1.00    4.00    --  111.00 -65.00 -28.38   26
 17  \w     90.00 116.00   1.00    4.00    --  111.00-111.00 -60.00   26
 18  \w     94.00 128.00   1.00    4.00    --  111.00 -61.00-120.00   34
 19  \w     89.00 124.00   1.00    4.00    --  111.00 -61.00-150.00   35
 20  \w     70.00 116.00   1.00    4.00    --  111.00-111.00-120.00   46
 21  \w     71.00  98.00   1.00    4.00    --  111.00 -94.00 -90.00   27
 22  \w     72.00 100.00   1.00    4.00    --  111.00 -77.00 -90.00   28
 23  \w     58.00  84.00   1.00    4.00    --  111.00 -94.00-150.00   26
 24  \w     50.00  76.00   1.00    4.00    --  111.00 -61.00-150.00   26
 25  \w     48.00  76.00   1.00    4.00    --  111.00 -61.00-120.00   28
 26  \w     48.00  74.00   1.00    4.00    --  111.00 -61.00 -90.00   26
 27  \w     41.00 132.00   1.00    4.00    --  111.00 -30.00 -30.00   91
 28  \w     91.00 152.00   1.00    4.00    --  111.00  15.00   0.00   61
 29  \w    128.00 154.00   1.00    4.00    --  111.00  61.00 -30.00   26
 30  \w    133.00 176.00   1.00    4.00    --  111.00  77.00 -90.00   43
 31  \w    153.00 178.00   1.00    4.00    --  111.00  30.00-150.00   25
 32  \w    136.00 173.00   1.00    4.00    --  111.00  45.00-120.00   37
 33  \w    130.00 162.00   1.00    4.00    --  111.00  61.00-180.00   32
 34  \w    121.00 146.00   1.00    4.00    --  111.00 111.00-150.00   25
 35  \w    106.00 136.00   1.00    4.00    --  111.00  61.00 -90.00   30
 36  \w     99.00 128.00   1.00    4.00    --  111.00  77.00 -90.00   29
 37  \w     93.00 125.00   1.00    4.00    --  111.00  61.00 -30.00   32
 38  \w    103.00 178.00   1.00    4.00    --  111.00  30.00  30.00   75
 39  \w    123.00 169.00   1.00    4.00    --  111.00  15.00 120.00   46
 40  \w     98.00 146.00   1.00    4.00    --  111.00  30.00 150.00   48
 41  \w     95.00 147.00   1.00    4.00    --  111.00  45.00 150.00   52
 42  \w     93.00 119.00   1.00    4.00    --  111.00  15.00 120.00   26
 43  \w     65.00 136.00   1.00    4.00    --  111.00 -25.00 135.98   71
 44  \w     79.00 104.00   1.00    4.00    --  111.00 -84.00 174.39   25
 45  \w     88.00 115.00   1.00    4.00    --  111.00-111.00 150.00   27
 46  \w     69.00 112.00   1.00    4.00    --  111.00-100.00 134.32   43
 47  \w     53.00  81.00   1.00    4.00    --  111.00-111.00  30.00   28
 48  \w     48.00  75.00   1.00    4.00    --  111.00 -94.00  60.00   27
 49  \w     50.00 106.00   1.00    4.00    --  111.00-111.00 120.00   56
 50  \w     46.00  72.00   1.00    4.00    --  111.00 -61.00   0.00   26
 51  \w     51.00  82.00   1.00    4.00    --  111.00 -61.00  30.00   31
 52  \w     51.00  77.00   1.00    4.00    --  111.00 -61.00  90.00   26
 53  \w     44.00 107.00   1.00    4.00    --  111.00 -45.00 120.00   63
 54  \w     41.00  67.00   1.00    4.00    --  111.00-111.00   0.00   26
 55  \w     44.00  86.00   1.00    4.00    --  111.00 -94.00   0.00   42
 56  \w     43.00  69.00   1.00    4.00    --  111.00 -94.00 -90.00   26
 57  \w     44.00 100.00   1.00    4.00    --  111.00 -94.00-120.00   56
 58  \w     50.00  75.00   1.00    4.00    --  111.00-111.00-180.00   25
 59  \w     48.00 114.00   1.00    4.00    --  111.00-111.00-150.00   66
 60  \w     42.00 109.00   1.00    4.00    --  111.00 -94.00  30.00   67
 61  \w     45.00  93.00   1.00    4.00    --  111.00 -94.00 150.00   48
 62  \w     43.00  76.00   1.00    4.00    --  111.00 -94.00 120.00   33
 63  \w     96.00 149.00   1.00    4.00    --  111.00  45.00   0.00   53
 64  \w     91.00 143.00   1.00    4.00    --  111.00  30.00-150.00   52
 65  \w     75.00 101.00   1.00    4.00    --  111.00  15.00-180.00   26
 66  \w    125.00 150.00   1.00    4.00    --  111.00 178.00   0.00   25
 67  \w     76.00 102.00   1.00    4.00    --  111.00 178.00   0.00   26
 68  \w     64.00 104.00   1.00    4.00    --  111.00 178.00 120.00   40
 69  \w   -109.00 -38.00   1.00    1.00    --  -36.45-178.00  60.00   71
;
_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      0.1367122000
_diffrn_orient_matrix_UB_12      0.0789068000
_diffrn_orient_matrix_UB_13      0.0226623000
_diffrn_orient_matrix_UB_21      -0.0481577000
_diffrn_orient_matrix_UB_22      0.1443046000
_diffrn_orient_matrix_UB_23      -0.0372154000
_diffrn_orient_matrix_UB_31      -0.1179854000
_diffrn_orient_matrix_UB_32      0.0452011000
_diffrn_orient_matrix_UB_33      0.0409305000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            26842
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.904
_diffrn_reflns_theta_min         3.430
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.324
_exptl_absorpt_correction_T_max  0.717
_exptl_absorpt_correction_T_min  0.227
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.792
_exptl_crystal_description       plate
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.025
_refine_diff_density_max         2.283
_refine_diff_density_min         -1.451
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     449
_refine_ls_number_reflns         7729
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0250P)^2^+5.6096P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0695
_refine_ls_wR_factor_ref         0.0703
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7450
_reflns_number_total             7729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02716_si_002.cif
_cod_data_source_block           DMSO
_cod_database_code               4132275
_chemical_oxdiff_formula         'Ir S O2 C20 H29'
_reflns_odcompleteness_completeness 97.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.83
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C8(H8), C4(H4), C5(H5), C8(H8)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              58364
_shelx_hkl_checksum              93965
_shelx_shelxl_version_number     2014/7
_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 1.660
_oxdiff_exptl_absorpt_empirical_full_min 0.686