Mechanistic Insight into Catalytic Redox-Neutral C-H Bond Activation Involving Manganese(I) Carbonyls: Catalyst Activation, Turnover, and Deactivation Pathways Reveal an Intricate Network of Steps.
Hammarback, L. Anders; Robinson, Alan; Lynam, Jason M.; Fairlamb, Ian J. S.; Journal of the American Chemical Society 141 (2019) 2316–2328; doi:10.1021/jacs.8b09095

data_4128177
_publ_section_title
;
 Mechanistic Insight into Catalytic Redox-Neutral C-H Bond Activation
 Involving Manganese(I) Carbonyls: Catalyst Activation, Turnover, and
 Deactivation Pathways Reveal an Intricate Network of Steps.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2316
_journal_page_last               2328
_journal_paper_doi               10.1021/jacs.8b09095
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C28 H18 Mn N O3'
_chemical_formula_sum            'C28 H18 Mn N O3'
_chemical_formula_weight         471.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.1024(2)
_cell_length_b                   7.84458(12)
_cell_length_c                   32.2257(5)
_cell_measurement_reflns_used    3290
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      70.7840
_cell_measurement_theta_min      5.3750
_cell_volume                     4829.03(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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_environment      N~2~
_diffrn_ambient_temperature      109.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_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     36.00  69.00   1.00    3.50    --    0.00  57.00 -60.00   33
  2  \w     31.00 126.00   1.00   14.00    --   54.00  37.00 -60.00   95
  3  \w    123.00 178.00   1.00   14.00    --  108.00 111.00 -60.00   55
  4  \w     92.00 154.00   1.00   14.00    --  108.00  50.00 120.00   62
  5  \w     61.00 126.00   1.00   14.00    --  108.00 -25.00 150.00   65
  6  \w     38.00 111.00   1.00   14.00    --  108.00-111.00 -60.00   73
  7  \w    -19.00   8.00   1.00    3.50    --    0.00  57.00 -60.00   27
  8  \w    -14.00  81.00   1.00   14.00    --   54.00 -77.00 -30.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0725511000
_diffrn_orient_matrix_UB_12      0.0085825000
_diffrn_orient_matrix_UB_13      0.0207920000
_diffrn_orient_matrix_UB_21      0.0351782000
_diffrn_orient_matrix_UB_22      0.0045232000
_diffrn_orient_matrix_UB_23      0.0429794000
_diffrn_orient_matrix_UB_31      0.0024022000
_diffrn_orient_matrix_UB_32      0.1961974000
_diffrn_orient_matrix_UB_33      -0.0019059000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            9268
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.589
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.674
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.312
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       plate
_exptl_crystal_F_000             1936
_exptl_crystal_recrystallization_method
'Evaporation of dichloromethane/pentane'
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.383
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         4294
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0403P)^2^+6.1898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1022
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3328
_reflns_number_total             4294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09095_si_002.cif
_cod_data_source_block           ijsf1809
_cod_database_code               4128177
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C28.5 H19 Cl Mn1 N1 O3'
_chemical_oxdiff_usercomment     'Anders LAH-10-732'
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.360
_reflns_odcompleteness_completeness 99.21
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
;
_shelx_res_checksum              41158
_shelx_hkl_checksum              4186
_shelx_fab_checksum              74358
_olex2_date_sample_data_collection 2018-04-04
_olex2_date_sample_submission    2018-03-22
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id LAH-10-732
_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 1.272
_oxdiff_exptl_absorpt_empirical_full_min 0.868