Mechanistic Insights into the Enantioselective Epoxidation of Olefins by Bioinspired Manganese Complexes: Role of Carboxylic Acid and Nature of Active Oxidant
Du, Junyi; Miao, Chengxia; Xia, Chungu; Lee, Yong-Min; Nam, Wonwoo; Sun, Wei; ACS Catalysis 8 (2018) 4528–; doi:10.1021/acscatal.8b00874

data_4515587
_publ_section_title
;
 Mechanistic Insights into the Enantioselective Epoxidation of Olefins by
 Bioinspired Manganese Complexes: Role of Carboxylic Acid and Nature of
 Active Oxidant
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4528
_journal_paper_doi               10.1021/acscatal.8b00874
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H28 F6 Mn N4 O6 S2'
_chemical_formula_sum            'C26 H28 F6 Mn N4 O6 S2'
_chemical_formula_weight         725.58
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.28107(17)
_cell_length_b                   18.28107(17)
_cell_length_c                   36.9230(5)
_cell_measurement_reflns_used    19029
_cell_measurement_temperature    173
_cell_measurement_theta_max      69.8850
_cell_measurement_theta_min      3.6240
_cell_volume                     12339.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      173
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_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    -15.00  63.00   1.00    2.00    --   54.00 -57.00  90.00   78
  2  \w     80.00 106.00   1.00    4.00    --  108.00 -99.00 157.00   26
  3  \w     87.00 113.00   1.00    4.00    --  108.00  50.00 150.00   26
  4  \w    126.00 154.00   1.00    4.00    --  108.00  74.00 154.86   28
  5  \w    125.00 177.00   1.00    4.00    --  108.00  77.00 120.00   52
  6  \w    100.00 158.00   1.00    4.00    --  108.00 111.00 -60.00   58
  7  \w    121.00 153.00   1.00    4.00    --  108.00  50.00-180.00   32
  8  \w    139.00 168.00   1.00    4.00    --  108.00  63.00-180.00   29
  9  \w    100.00 153.00   1.00    4.00    --  108.00 111.00-120.00   53
 10  \w    100.00 176.00   1.00    4.00    --  108.00 111.00 -90.00   76
 11  \w     86.00 112.00   1.00    4.00    --  108.00  50.00-180.00   26
 12  \w     84.00 176.00   1.00    4.00    --  108.00  38.00-150.00   92
 13  \w     84.00 110.00   1.00    4.00    --  108.00  43.00-177.28   26
 14  \w     82.00 107.00   1.00    4.00    --  108.00  38.00-180.00   25
 15  \w     86.00 112.00   1.00    4.00    --  108.00  63.00-180.00   26
 16  \w     79.00 104.00   1.00    4.00    --  108.00  77.00-180.00   25
 17  \w     83.00 109.00   1.00    4.00    --  108.00  40.00-157.33   26
 18  \w     79.00 105.00   1.00    4.00    --  108.00  25.00-180.00   26
 19  \w     75.00 109.00   1.00    4.00    --  108.00  25.00-150.00   34
 20  \w     61.00 123.00   1.00    2.00    --   54.00  57.00  30.00   62
 21  \w     78.00 104.00   1.00    4.00    --  108.00  77.00 120.00   26
 22  \w     86.00 112.00   1.00    4.00    --  108.00  63.00 150.00   26
 23  \w     86.00 112.00   1.00    4.00    --  108.00  62.00 179.09   26
 24  \w     78.00 104.00   1.00    4.00    --  108.00  77.00 150.00   26
 25  \w     81.00 107.00   1.00    4.00    --  108.00  74.00 154.86   26
 26  \w     33.00  73.00   1.00    2.00    --   54.00  57.00 150.00   40
 27  \w    -15.00  50.00   1.00    1.00    --    0.00  57.00  30.00   65
 28  \w     54.00 123.00   1.00    2.00    --   54.00  57.00-120.00   69
 29  \w     34.00  61.00   1.00    2.00    --   54.00  57.00-180.00   27
 30  \w     26.00  52.00   1.00    2.00    --   54.00  77.00-180.00   26
 31  \w    -38.00 -12.00   1.00    1.00    --    0.00 -57.00-180.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0689191000
_diffrn_orient_matrix_UB_12      0.0348887000
_diffrn_orient_matrix_UB_13      0.0167093000
_diffrn_orient_matrix_UB_21      0.0404460000
_diffrn_orient_matrix_UB_22      -0.0736893000
_diffrn_orient_matrix_UB_23      -0.0031751000
_diffrn_orient_matrix_UB_31      0.0267605000
_diffrn_orient_matrix_UB_32      0.0214911000
_diffrn_orient_matrix_UB_33      -0.0380862000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0497
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            64590
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        66.584
_diffrn_reflns_theta_max         66.584
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.498
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       needle
_exptl_crystal_F_000             5936
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.951
_refine_diff_density_min         -0.509
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 6794 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1675
_refine_ls_number_reflns         21223
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0577P)^2^+8.8574P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1154
_refine_ls_wR_factor_ref         0.1274
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.944
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                17666
_reflns_number_total             21223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b00874_si_002.cif
_cod_data_source_block           xu_0306
_cod_original_cell_volume        12339.6(3)
_cod_database_code               4515587
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.92
_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
2. Uiso/Uaniso restraints and constraints
Uanis(F23') \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C6BA)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F23') \\sim Ueq, Uanis(F23) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.008
3. Others
 Fixed Sof: S8(0.6) F22(0.6) F23(0.6) F24(0.6) O24(0.6) C104(0.6) S8'(0.4)
 F22'(0.4) F23'(0.4) F24'(0.4) O24'(0.4) C6BA(0.4)
4.a Ternary CH refined with riding coordinates:
 C15(H15), C35(H35), C62(H62), C82(H82)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C14(H14A,H14B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C33(H33A,H33B), C34(H34A,H34B), C36(H36A,H36B),
  C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C50(H50A,H50B), C58(H58A,
 H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C63(H63A,H63B),
 C64(H64A,H64B), C71(H71A,H71B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B),
  C83(H83A,H83B), C84(H84A,H84B), C91(H91A,H91B), C97(H97A,H97B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12),
 C13(H13), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47), C48(H48), C53(H53), C54(H54), C55(H55), C56(H56), C66(H66),
  C67(H67), C68(H68), C69(H69), C70(H70), C73(H73), C74(H74), C75(H75),
 C76(H76), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90), C93(H93), C94(H94),
  C95(H95), C96(H96), C99(H99), C100(H100), C101(H101), C102(H102)
;
_olex2_date_sample_data_collection 2018-03-06
_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 1.635
_oxdiff_exptl_absorpt_empirical_full_min 0.716