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_4132274
_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         'C24 H30 F3 Ir O'
_chemical_formula_sum            'C24 H30 F3 Ir O'
_chemical_formula_weight         583.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_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                90
_cell_angle_beta                 90.967(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5111(3)
_cell_length_b                   23.1376(7)
_cell_length_c                   8.0997(2)
_cell_measurement_reflns_used    7642
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      27.5860
_cell_measurement_theta_min      3.9210
_cell_volume                     2156.96(10)
_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      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.915
_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     -5.00  44.00   1.00    1.00    --  -14.01  57.00  90.00   49
  2  \w     40.00  73.00   1.00    1.00    --   16.51  37.00 120.00   33
  3  \w      3.00  79.00   1.00    1.00    --   16.51  57.00  60.00   76
  4  \w      6.00  82.00   1.00    1.00    --   16.51  57.00 -30.00   76
  5  \w     12.00  78.00   1.00    1.00    --   16.51  37.00-180.00   66
  6  \w      2.00  80.00   1.00    1.00    --   16.51  57.00-120.00   78
  7  \w    -29.00  52.00   1.00    1.00    --  -14.01  77.00 -60.00   81
  8  \w    -71.00 -44.00   1.00    1.00    --  -14.01 132.00-136.48   27
  9  \w    -21.00  53.00   1.00    1.00    --   16.51 -98.00 161.43   74
 10  \w    -11.00  60.00   1.00    1.00    --   16.51-110.00  56.70   71
 11  \w    -20.00  53.00   1.00    1.00    --   16.51 -99.00-120.00   73
;
_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      0.0144704000
_diffrn_orient_matrix_UB_12      -0.0076208000
_diffrn_orient_matrix_UB_13      0.0826780000
_diffrn_orient_matrix_UB_21      -0.0597364000
_diffrn_orient_matrix_UB_22      0.0004841000
_diffrn_orient_matrix_UB_23      0.0201141000
_diffrn_orient_matrix_UB_31      -0.0047327000
_diffrn_orient_matrix_UB_32      -0.0296720000
_diffrn_orient_matrix_UB_33      -0.0208486000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0891
_diffrn_reflns_av_unetI/netI     0.0719
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.915
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            33847
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.600
_diffrn_reflns_theta_min         3.522
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.228
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_correction_T_min  0.280
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.797
_exptl_crystal_description       plate
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.029
_refine_diff_density_max         2.637
_refine_diff_density_min         -1.544
_refine_diff_density_rms         0.229
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     312
_refine_ls_number_reflns         5555
_refine_ls_number_restraints     189
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0400
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0132P)^2^+4.8719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0655
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4375
_reflns_number_total             5555
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02716_si_003.cif
_cod_data_source_block           piallyl
_cod_original_cell_volume        2156.97(11)
_cod_database_code               4132274
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C24 H28 Ir F3 O'
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 C2-H2
 0.99 with sigma of 0.02
 C3-H3
 0.99 with sigma of 0.02
 H2-C1 \\sim H2-C3
 with sigma of 0.02
 H3-C2 \\sim H3-C4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C16, C19, F20, F21, F22, C19B, F20B, F21B, F22B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C16, C17, C18, C19B, F20B, F21B, F22B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C16, C17, C18, C19, F20, F21, F22}
6. Others
 Sof(C19B)=Sof(F20B)=Sof(F21B)=Sof(F22B)=1-FVAR(1)
 Sof(C19)=Sof(F20)=Sof(F21)=Sof(F22)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C11(H11A,H11B)
7.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C17(H17), C18(H18)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C)
;
_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 1.337
_oxdiff_exptl_absorpt_empirical_full_min 0.713