Efficient benzylic and aliphatic C-h oxidation with selectivity for methylenic sites catalyzed by a bioinspired manganese complex.
Shen, Duyi; Miao, Chengxia; Wang, Shoufeng; Xia, Chungu; Sun, Wei; Organic letters 16 (2014) 1108–1111; doi:10.1021/ol4037083

data_1513428
_publ_section_title
;
 Efficient benzylic and aliphatic C-h oxidation with selectivity for
 methylenic sites catalyzed by a bioinspired manganese complex.
;
_journal_issue                   4
_journal_name_full               'Organic letters'
_journal_page_first              1108
_journal_page_last               1111
_journal_paper_doi               10.1021/ol4037083
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H30 F6 Mn N6 O6 S2'
_chemical_formula_sum            'C26 H30 F6 Mn N6 O6 S2'
_chemical_formula_weight         755.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-04-12
_audit_creation_method
;
  Olex2 1.2
  (compiled Mar 21 2013 11:16:32, GUI svn.r4456)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.352(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   8.5432(2)
_cell_length_b                   16.2125(4)
_cell_length_c                   11.4680(5)
_cell_measurement_reflns_used    7596
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      28.3520
_cell_measurement_theta_min      3.7630
_cell_volume                     1588.36(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9979
_diffrn_measured_fraction_theta_max 0.8462
_diffrn_measurement_details
;
  1 omega   -7.00   59.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   77.0000   90.0000 66

  2 omega   61.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   77.0000 -150.0000 27

  3 omega    9.00   74.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   77.0000  -30.0000 65

  4 omega   -7.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075   77.0000 -150.0000 70

  5 omega  -28.00   16.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  -77.0000   60.0000 44

  6 omega   -4.00   22.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000 -120.0000 26

  7 omega  -43.00   -3.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  -77.0000 -180.0000 40

  8 omega   77.00  105.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  178.0000  -90.0000 28

  9 omega   -2.00   31.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075   57.0000  -30.0000 33

 10 omega   40.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075    0.0000  150.0000 58

 11 omega  -27.00   -1.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075    0.0000  150.0000 26
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0263227000
_diffrn_orient_matrix_UB_12      0.0105155000
_diffrn_orient_matrix_UB_13      -0.0566020000
_diffrn_orient_matrix_UB_21      0.0769560000
_diffrn_orient_matrix_UB_22      -0.0125523000
_diffrn_orient_matrix_UB_23      0.0155791000
_diffrn_orient_matrix_UB_31      -0.0169871000
_diffrn_orient_matrix_UB_32      -0.0406111000
_diffrn_orient_matrix_UB_33      -0.0194111000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13156
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.98
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.633
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84119
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.580
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             774
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.013(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         6173
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0324
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+0.4540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0698
_refine_ls_wR_factor_ref         0.0717
_reflns_number_gt                5824
_reflns_number_total             6173
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol4037083_si_002.cif
_cod_data_source_block           exp_914
_cod_original_cell_volume        1588.37(8)
_cod_database_code               1513428
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C17(H17), C18(H18), C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;