Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates
Sandl, Sebastian; Maier, Thomas M.; van Leest, Nicolaas P.; Kröncke, Susanne; Chakraborty, Uttam; Demeshko, Serhiy; Koszinowski, Konrad; de Bruin, Bas; Meyer, Franc; Bodensteiner, Michael; Herrmann, Carmen; Wolf, Robert; Jacobi von Wangelin, Axel; ACS Catalysis 9 (2019) 7596–; doi:10.1021/acscatal.9b01584

data_4514646
_publ_section_title
;
 Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride
 Intermediates
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              7596
_journal_paper_doi               10.1021/acscatal.9b01584
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C36 H40 Br2 Co N2'
_chemical_formula_sum            'C36 H40 Br2 Co N2'
_chemical_formula_weight         719.45
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-16
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.047(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.0266(7)
_cell_length_b                   12.0329(2)
_cell_length_c                   22.8033(6)
_cell_measurement_reflns_used    13853
_cell_measurement_temperature    123(1)
_cell_measurement_theta_max      73.4410
_cell_measurement_theta_min      4.1060
_cell_volume                     6823.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_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      123(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.954
_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    -38.00  74.00   1.00    5.50    --   40.71 -77.00  30.00  112
  2  \w     11.00 117.00   1.00    5.50    --   40.71  77.00-150.00  106
  3  \w     23.00  63.00   1.00   22.00    --  106.98 -94.00 120.00   40
  4  \w     29.00  69.00   1.00   22.00    --  106.98 -30.00 -90.00   40
  5  \w     77.00 157.00   1.00   22.00    --  106.98  61.00-120.00   80
  6  \w     34.00 109.00   1.00   22.00    --  106.98 -94.00-180.00   75
  7  \w     35.00  69.00   1.00   22.00    --  106.98 -30.00 -60.00   34
  8  \w     82.00 109.00   1.00   22.00    --  106.98 -94.00 120.00   27
  9  \w     28.00 108.00   1.00   22.00    --  106.98 -94.00  30.00   80
 10  \w     78.00 158.00   1.00   22.00    --  106.98 125.00  60.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0135819000
_diffrn_orient_matrix_UB_12      -0.1244996000
_diffrn_orient_matrix_UB_13      0.0013284000
_diffrn_orient_matrix_UB_21      0.0583685000
_diffrn_orient_matrix_UB_22      0.0244559000
_diffrn_orient_matrix_UB_23      0.0456919000
_diffrn_orient_matrix_UB_31      -0.0158080000
_diffrn_orient_matrix_UB_32      -0.0165733000
_diffrn_orient_matrix_UB_33      0.0574246000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0735
_diffrn_reflns_av_unetI/netI     0.0749
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24613
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.616
_diffrn_reflns_theta_min         3.554
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.871
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.07166
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.37b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             2936
_exptl_crystal_size_max          0.764
_exptl_crystal_size_mid          0.286
_exptl_crystal_size_min          0.211
_refine_diff_density_max         1.801
_refine_diff_density_min         -1.563
_refine_diff_density_rms         0.202
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     755
_refine_ls_number_reflns         13116
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0892
_refine_ls_R_factor_gt           0.0857
_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^)+(0.1638P)^2^+15.4811P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2360
_refine_ls_wR_factor_ref         0.2404
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12117
_reflns_number_total             13116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01584_si_002.cif
_cod_data_source_block           mp_neu
_cod_database_code               4514646
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72 H80 N4 Co2 Br4'
_reflns_odcompleteness_completeness 98.28
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C31(H31), C34(H34), C55(H55), C58(H58), C67(H67), C70(H70)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16),
 C17(H17), C27(H27), C28(H28), C29(H29), C40(H40), C41(H41), C42(H42), C44(H44),
  C45(H45), C46(H46), C51(H51), C52(H52), C53(H53), C63(H63), C64(H64), C65(H65)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C71(H71A,H71B,
 H71C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              867
_shelx_hkl_checksum              62226
_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 4.664
_oxdiff_exptl_absorpt_empirical_full_min 0.354