Intermediates and mechanism in iron-catalyzed C–H methylation with trimethylaluminum
Bhatia, Shilpa; DeMuth, Joshua C.; Neidig, Michael L.; Chemical Communications  (2021) –; doi:10.1039/D1CC05607G

data_7129257
_publ_section_title
;
 Intermediates and mechanism in iron-catalyzed C--H methylation with
 trimethylaluminum
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05607G
_journal_year                    2021
_chemical_formula_moiety         'C54 H50 Fe P4'
_chemical_formula_sum            'C54 H50 Fe P4'
_chemical_formula_weight         878.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-08-23
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-09-22 deposited with the CCDC.	2021-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.6965(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.40452(13)
_cell_length_b                   26.0935(3)
_cell_length_c                   19.63981(19)
_cell_measurement_reflns_used    24188
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7820
_cell_measurement_theta_min      3.3670
_cell_volume                     5804.62(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_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   -120.00 -42.00   0.50    0.71    --  -47.29-169.00 166.00  156
  2  \w    -87.00  -3.00   0.50    0.71    --  -47.29 115.00  40.00  168
  3  \w     64.00 120.00   0.50    0.71    --   47.29 169.00-176.00  112
  4  \w     24.00  90.00   0.50    0.71    --   47.29-115.00 -49.00  132
  5  \w   -163.00 -77.00   0.50    2.86    --  -91.75-115.00 -49.00  172
  6  \w   -123.00 -32.00   0.50    2.86    --  -91.75 169.00-176.00  182
  7  \w    -86.00 -19.00   0.50    2.86    --  -91.75 115.00  40.00  134
  8  \w     54.00 149.00   0.50    2.86    --  113.25-169.00 166.00  190
  9  \w     42.00 112.00   0.50    2.86    --  113.25-115.00 -49.00  140
 10  \w     98.00 178.00   0.50    2.86    --  113.25 115.00  40.00  160
 11  \w     64.00 157.00   0.50    2.86    --  113.25 169.00-176.00  186
 12  \w     -3.00  28.00   0.50    0.71    --  -47.29  19.00   0.00   62
 13  \w   -120.00 -70.00   0.50    0.71    --  -47.29-125.00   0.00  100
 14  \w     -3.00  28.00   0.50    0.71    --  -47.29  19.00 -30.00   62
 15  \w     -3.00  28.00   0.50    0.71    --  -47.29  19.00-120.00   62
 16  \w    -27.00  10.00   0.50    0.71    --   47.29 -19.00 -30.00   74
 17  \w    -27.00  10.00   0.50    0.71    --   47.29 -19.00  30.00   74
 18  \w    101.00 178.00   0.50    2.86    --  113.25  30.00  30.00  154
 19  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00-150.00   76
 20  \w     97.00 178.00   0.50    2.86    --  113.25  61.00 -60.00  162
 21  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00  30.00   76
 22  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00-180.00   76
 23  \w     92.00 178.00   0.50    2.86    --  113.25 125.00 120.00  172
 24  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00 -60.00   76
 25  \w     42.00 109.00   0.50    2.86    --  113.25 -94.00 -30.00  134
 26  \w    101.00 178.00   0.50    2.86    --  113.25  45.00  90.00  154
 27  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00   0.00   76
 28  \w     42.00 117.00   0.50    2.86    --  113.25-125.00 150.00  150
 29  \w     42.00  80.00   0.50    2.86    --  113.25 -61.00 -30.00   76
 30  \w     42.00 109.00   0.50    2.86    --  113.25 -94.00   0.00  134
 31  \w     97.00 178.00   0.50    2.86    --  113.25  61.00 120.00  162
 32  \w     25.00 120.00   0.50    0.71    --   47.29  77.00 -30.00  190
 33  \w     32.00 120.00   0.50    0.71    --   47.29  57.00 -60.00  176
 34  \w     25.00 120.00   0.50    0.71    --   47.29  77.00-150.00  190
 35  \w     32.00 120.00   0.50    0.71    --   47.29  57.00-180.00  176
 36  \w     32.00 120.00   0.50    0.71    --   47.29  57.00  60.00  176
 37  \w     25.00 120.00   0.50    0.71    --   47.29  77.00  90.00  190
 38  \w    100.00 172.00   0.50    2.86    --  113.25  15.00-150.00  144
 39  \w     42.00  78.00   0.50    2.86    --  113.25 -61.00 150.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0044010000
_diffrn_orient_matrix_UB_12      0.0580014000
_diffrn_orient_matrix_UB_13      -0.0145997000
_diffrn_orient_matrix_UB_21      0.1063826000
_diffrn_orient_matrix_UB_22      -0.0052458000
_diffrn_orient_matrix_UB_23      -0.0412065000
_diffrn_orient_matrix_UB_31      -0.0846407000
_diffrn_orient_matrix_UB_32      -0.0095893000
_diffrn_orient_matrix_UB_33      -0.0657977000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0761
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            48565
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.310
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.336
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.005
_exptl_crystal_description       block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.295
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.900
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     279
_refine_ls_number_reflns         6239
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0464
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0709P)^2^+5.9919P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1243
_refine_ls_wR_factor_ref         0.1262
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5773
_reflns_number_total             6239
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05607g2.cif
_cod_data_source_block           neijd07
_cod_database_code               7129257
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
  C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
;
_shelx_res_checksum              92473
_shelx_fab_checksum              49598
_olex2_submission_original_sample_id neijd07
_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 3.542
_oxdiff_exptl_absorpt_empirical_full_min 0.495