Cobalt(II)-Catalyzed Activation of C(sp3)–H Bonds: Organic Oxidant Enabled Selective Functionalization
Zhang, He; Sun, Meng-Chan; Yang, Dandan; Li, Tong; Song, Mao-Ping; Niu, Jun-Long; ACS Catalysis  (2022) 1650–1656; doi:10.1021/acscatal.1c05250

data_4519294
_publ_section_title
;
 Cobalt(II)-Catalyzed Activation of C(sp3)--H Bonds: Organic Oxidant
 Enabled Selective Functionalization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1650
_journal_page_last               1656
_journal_paper_doi               10.1021/acscatal.1c05250
_journal_year                    2022
_chemical_formula_moiety         'C51 H59 Co N4 O11 S2'
_chemical_formula_sum            'C51 H60 Co N4 O11 S2'
_chemical_formula_weight         1028.08
_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   geom
_audit_creation_date             2021-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.540(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1519(4)
_cell_length_b                   27.2945(8)
_cell_length_c                   14.7065(4)
_cell_measurement_reflns_used    6689
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      71.2780
_cell_measurement_theta_min      3.2450
_cell_volume                     5233.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (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      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -31.00  43.00   0.50    1.00    --    0.00  82.00  60.00  148
  2  \w      9.00  59.00   0.50    1.00    --    0.00  57.00  30.00  100
  3  \w     -6.00  32.00   0.50    1.00    --    0.00  57.00 -30.00   76
  4  \w     75.00 103.00   0.50   13.00    --   95.80  45.00 -60.00   56
  5  \w     73.00 105.00   0.50   13.00    --   95.80 -61.00  90.00   64
  6  \w      7.00 128.00   0.50   13.00    --   95.80 -82.00 150.00  242
  7  \w     73.00 120.00   0.50   13.00    --   95.80 -82.00-150.00   94
  8  \w     88.00 128.00   0.50   13.00    --   95.80 -82.00-120.00   80
  9  \w     15.00 114.00   0.50   13.00    --   95.80 -30.00 -30.00  198
 10  \w      6.00  64.00   0.50   13.00    --   95.80 -61.00  90.00  116
 11  \w    122.00 185.00   0.50   13.00    --   95.80  45.00 -60.00  126
 12  \w     82.00 107.00   0.50   13.00    --   95.80  30.00-180.00   50
 13  \w    117.00 180.00   0.50   13.00    --   95.80  30.00-180.00  126
 14  \w     83.00 123.00   0.50   13.00    --   95.80 -82.00 -90.00   80
 15  \w     27.00 102.00   0.50   13.00    --   95.80 -61.00  30.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1160910000
_diffrn_orient_matrix_UB_12      0.0026890000
_diffrn_orient_matrix_UB_13      0.0324813000
_diffrn_orient_matrix_UB_21      -0.0048229000
_diffrn_orient_matrix_UB_22      0.0563420000
_diffrn_orient_matrix_UB_23      -0.0048202000
_diffrn_orient_matrix_UB_31      -0.0213874000
_diffrn_orient_matrix_UB_32      0.0018860000
_diffrn_orient_matrix_UB_33      0.1004670000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            32119
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        65.996
_diffrn_reflns_theta_max         65.996
_diffrn_reflns_theta_min         3.238
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.821
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92279
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_description       block
_exptl_crystal_F_000             2164
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.755
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         9103
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0762
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1219P)^2^+3.5352P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2147
_refine_ls_wR_factor_ref         0.2296
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6064
_reflns_number_total             9103
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05250_si_003.cif
_cod_data_source_block           hy
_cod_database_code               4519294
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.701
_shelx_estimated_absorpt_t_min   0.515
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C22(H22), C24(H24), C26(H26), C49(H49)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B), C10(H10A,H10B), C11(H11A,
 H11B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,H25B), C27(H27A,H27B),
 C28(H28A,H28B), C29(H29A,H29B)
3.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C16(H16), C17(H17), C31(H31), C32(H32), C34(H34),
 C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C44(H44), C45(H45), C46(H46),
  C47(H47)
3.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C1AA(H1AA,H1AB,
 H1AC)
;
_shelx_res_checksum              37775
_shelx_hkl_checksum              14019
_shelx_fab_checksum              60534
_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 1.167
_oxdiff_exptl_absorpt_empirical_full_min 0.877