Mechanism of the Bis(imino)pyridine-Iron-Catalyzed Hydromagnesiation of Styrene Derivatives.
Neate, Peter G. N.; Greenhalgh, Mark D.; Brennessel, William W.; Thomas, Stephen P.; Neidig, Michael L.; Journal of the American Chemical Society 141 (2019) 10099–10108; doi:10.1021/jacs.9b04869

data_4128291
_publ_section_title
;
 Mechanism of the Bis(imino)pyridine-Iron-Catalyzed Hydromagnesiation of
 Styrene Derivatives.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10099
_journal_page_last               10108
_journal_paper_doi               10.1021/jacs.9b04869
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C41 H52 Fe N5, C20 H40 Br0.60 Cl0.40 Mg O5'
_chemical_formula_sum            'C61 H92 Br0.6 Cl0.4 Fe Mg N5 O5'
_chemical_formula_weight         1117.79
_chemical_name_common            neipn21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.6754(5)
_cell_length_b                   12.3150(7)
_cell_length_c                   24.0776(7)
_cell_measurement_reflns_used    7618
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      71.35
_cell_measurement_theta_min      4.30
_cell_volume                     6723.6(5)
_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    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.957
_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    -50.00  20.00   0.50   17.89    --  -49.37  19.00-150.00  140
  2  \w    -74.00 -24.00   0.50   71.56    --  -84.25 138.00  -7.00  100
  3  \w    -97.00 -59.00   0.50   17.89    --  -49.37 138.00  -7.00   76
  4  \w    -38.00 -13.00   0.50   71.56    --  -84.25  15.00  60.00   50
  5  \w   -119.00 -31.00   0.50   17.89    --  -49.37 -77.00 120.00  176
  6  \w   -120.00 -63.00   0.50   17.89    --  -49.37-138.00 -69.00  114
  7  \w     46.00  71.00   0.50   17.89    --   49.37-138.00 -69.00   50
  8  \w     61.00  86.00   0.50   71.56    --  105.75-138.00 -69.00   50
  9  \w     58.00 108.00   0.50   71.56    --  105.75 -94.00-180.00  100
 10  \w     34.00  67.00   0.50   71.56    --  105.75 -30.00 -90.00   66
 11  \w     34.00  71.00   0.50   71.56    --  105.75 -30.00 -60.00   74
 12  \w     35.00  72.00   0.50   71.56    --  105.75 -30.00-150.00   74
 13  \w     41.00  72.00   0.50   71.56    --  105.75 -30.00  60.00   62
 14  \w     45.00  77.00   0.50   71.56    --  105.75 -45.00  90.00   64
 15  \w     35.00 108.00   0.50   71.56    --  105.75 -94.00  90.00  146
 16  \w     78.00 122.00   0.50   71.56    --  105.75-131.00 105.00   88
 17  \w    107.00 132.00   0.50   71.56    --  105.75 138.00  -7.00   50
 18  \w    110.00 135.00   0.50   71.56    --  105.75 131.00 176.00   50
;
_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      0.0051782000
_diffrn_orient_matrix_UB_12      -0.0779601000
_diffrn_orient_matrix_UB_13      -0.0499185000
_diffrn_orient_matrix_UB_21      0.0036683000
_diffrn_orient_matrix_UB_22      -0.0975091000
_diffrn_orient_matrix_UB_23      0.0399611000
_diffrn_orient_matrix_UB_31      -0.0675449000
_diffrn_orient_matrix_UB_32      -0.0108310000
_diffrn_orient_matrix_UB_33      -0.0017078000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0533
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            33365
_diffrn_reflns_point_group_measured_fraction_full 0.911
_diffrn_reflns_point_group_measured_fraction_max 0.851
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.434
_diffrn_reflns_theta_min         3.589
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.804
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.104
_exptl_crystal_description       plate
_exptl_crystal_F_000             2395
_exptl_crystal_size_max          0.354
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.077
_refine_diff_density_max         1.239
_refine_diff_density_min         -0.928
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.112(9)
_refine_ls_extinction_coef       0.00052(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         12301
_refine_ls_number_restraints     131
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1008
_refine_ls_R_factor_gt           0.0753
_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^)+(0.1413P)^2^+2.3856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2054
_refine_ls_wR_factor_ref         0.2282
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_full    0.819
_reflns_Friedel_fraction_max     0.739
_reflns_number_gt                8676
_reflns_number_total             12301
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04869_si_003.cif
_cod_data_source_block           neipn21
_cod_original_formula_sum        'C61 H92 Br0.60 Cl0.40 Fe Mg N5 O5'
_cod_database_code               4128291
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.437
_shelx_estimated_absorpt_t_max   0.813
_shelx_res_checksum              7918
_shelx_hkl_checksum              86615
_shelx_fab_checksum              84565