Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds in the Presence of Electronically Activated C-H Bonds.
Liu, Wenbin; Ren, Zhi; Bosse, Aaron T.; Liao, Kuangbiao; Goldstein, Elizabeth L.; Bacsa, John; Musaev, Djamaladdin G.; Stoltz, Brian M.; Davies, Huw M. L.; Journal of the American Chemical Society 140 (2018) 12247–12255; doi:10.1021/jacs.8b07534

data_4132945
_publ_section_title
;
 Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds
 in the Presence of Electronically Activated C-H Bonds.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12247
_journal_page_last               12255
_journal_paper_doi               10.1021/jacs.8b07534
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C88 H60 Br4 Cl4 O8 Rh2'
_chemical_formula_sum            'C88 H64 Br4 Cl4 O10 Rh2'
_chemical_formula_weight         1948.61
_space_group_crystal_system      tetragonal
_space_group_IT_number           90
_space_group_name_Hall           'P 4ab 2ab'
_space_group_name_H-M_alt        'P 4 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-25
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2018.05.31 svn.r3508 for OlexSys, GUI svn.r5510)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4695(6)
_cell_length_b                   20.4695(6)
_cell_length_c                   19.2209(8)
_cell_measurement_reflns_used    14776
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5090
_cell_measurement_theta_min      1.7800
_cell_volume                     8053.6(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     57.24 189.24   0.50  119.97    --   20.83  73.80 -68.38  264
  2  \w    -18.76 189.24   0.50  119.97    --   20.83  73.80 147.53  416
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0340366000
_diffrn_orient_matrix_UB_12      0.0048891000
_diffrn_orient_matrix_UB_13      0.0046534000
_diffrn_orient_matrix_UB_21      0.0015944000
_diffrn_orient_matrix_UB_22      -0.0165322000
_diffrn_orient_matrix_UB_23      0.0323710000
_diffrn_orient_matrix_UB_31      0.0064278000
_diffrn_orient_matrix_UB_32      0.0300459000
_diffrn_orient_matrix_UB_33      0.0170719000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1306
_diffrn_reflns_av_unetI/netI     0.0899
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            40044
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.712
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_min         1.761
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           35
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           45
_exptl_absorpt_coefficient_mu    2.586
_exptl_absorpt_correction_T_max  0.65996
_exptl_absorpt_correction_T_min  0.65241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.607
_exptl_crystal_description       needle
_exptl_crystal_F_000             3880
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of ethyl acetate and hexane  by slow evaporation'
_exptl_crystal_size_max          0.591
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.032
_refine_diff_density_max         1.526
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Flack x determined using 1584 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.015(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         6882
_refine_ls_number_restraints     478
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0938
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0559P)^2^+12.6996P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1166
_refine_ls_wR_factor_ref         0.1273
_reflns_Friedel_coverage         0.760
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4969
_reflns_number_total             6882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07534_si_005.cif
_cod_data_source_block           wl-n2-137-27
_cod_original_cell_volume        8053.5(6)
_cod_database_code               4132945
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C352  H256  Br16  Cl16  O40  Rh8  '
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.310
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid body (RIGU) restrains
 Br1_1, Cl1_1, O1_1, O2_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1,
 C9_1, C10_1, C11_1, C12_1, C13_1, C14_1, C15_1, C16_1, C17_1, C18_1, C19_1,
 C20_1, C21_1, C22_1
 Br1_2, Cl1_2, O1_2, O2_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2,
 C9_2, C10_2, C11_2, C12_2, C13_2, C14_2, C15_2, C16_2, C17_2, C18_2, C19_2,
 C20_2, C21_2, C22_2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
3. Same fragment restrains
{Br1_2, Cl1_2, O1_2, O2_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2,
C9_2, C10_2, C11_2, C12_2, C13_2, C14_2, C15_2, C16_2, C17_2, C18_2, C19_2,
C20_2, C21_2, C22_2}
as
{Br1_1, Cl1_1, O1_1, O2_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1,
C9_1, C10_1, C11_1, C12_1, C13_1, C14_1, C15_1, C16_1, C17_1, C18_1, C19_1,
C20_1, C21_1, C22_1} sigma for 1-2: 0.002 1-3: 0.004
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9(H9A,H9B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C5(H5), C7(H7), C8(H8),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20),
  C21(H21), C22(H22)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop with paratone oil'
_olex2_submission_original_sample_id WL-N2-137-27
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.966
_oxdiff_exptl_absorpt_empirical_full_min 0.706