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_4128289
_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
'C32 H32 Fe, C20 H40 Br0.69 Cl0.31 Mg O5, 3(C4 H8 O)'
_chemical_formula_sum            'C64 H96 Br0.69 Cl0.31 Fe Mg O8'
_chemical_formula_weight         1139.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-07-30
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                72.3390(10)
_cell_angle_beta                 80.7430(10)
_cell_angle_gamma                74.6990(10)
_cell_formula_units_Z            2
_cell_length_a                   11.94400(10)
_cell_length_b                   13.0469(2)
_cell_length_c                   21.0494(2)
_cell_measurement_reflns_used    23238
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.7850
_cell_measurement_theta_min      2.3080
_cell_volume                     3003.11(6)
_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, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.981
_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    -51.00  24.00   0.50    0.58    --  -49.62  19.00  30.00  150
  2  \w     43.00  70.00   0.50    0.58    --   49.62-129.00  18.00   54
  3  \w     54.00  81.00   0.50    2.33    --  105.75-129.00  18.00   54
  4  \w     71.00 107.00   0.50    2.33    --  105.75 -94.00  60.00   72
  5  \w     92.00 127.00   0.50    2.33    --  105.75 -77.00  30.00   70
  6  \w     87.00 116.00   0.50    2.33    --  105.75-125.00  60.00   58
  7  \w     74.00  99.00   0.50    2.33    --  105.75 -94.00 150.00   50
  8  \w     54.00  89.00   0.50    2.33    --  105.75 -45.00  60.00   70
  9  \w     53.00  90.00   0.50    2.33    --  105.75 -45.00  30.00   74
 10  \w     34.00  71.00   0.50    2.33    --  105.75 -30.00 -60.00   74
 11  \w     41.00  67.00   0.50    2.33    --  105.75 -45.00-120.00   52
 12  \w     39.00  72.00   0.50    2.33    --  105.75 -30.00-120.00   66
 13  \w     41.00  72.00   0.50    2.33    --  105.75 -30.00-150.00   62
 14  \w     35.00  82.00   0.50    2.33    --  105.75 -15.00-120.00   94
 15  \w    103.00 146.00   0.50    2.33    --  105.75  15.00-120.00   86
 16  \w    137.00 163.00   0.50    2.33    --  105.75  15.00-180.00   52
 17  \w    101.00 127.00   0.50    2.33    --  105.75  15.00-180.00   52
 18  \w     98.00 136.00   0.50    2.33    --  105.75  45.00 -90.00   76
 19  \w     84.00 131.00   0.50    2.33    --  105.75 140.00 -95.00   94
 20  \w    114.00 140.00   0.50    2.33    --  105.75 129.00  91.00   52
 21  \w    145.00 171.00   0.50    2.33    --  105.75 125.00 150.00   52
 22  \w     40.00  72.00   0.50    2.33    --  105.75 -30.00  30.00   64
 23  \w     34.00  64.00   0.50    2.33    --  105.75 -30.00  60.00   60
 24  \w     34.00  72.00   0.50    2.33    --  105.75 -30.00   0.00   76
 25  \w     36.00  77.00   0.50    2.33    --  105.75 -15.00   0.00   82
 26  \w     54.00 109.00   0.50    2.33    --  105.75 -94.00 -60.00  110
 27  \w     76.00 101.00   0.50    2.33    --  105.75-125.00 -60.00   50
 28  \w     63.00  89.00   0.50    2.33    --  105.75-125.00 -90.00   52
 29  \w     60.00 107.00   0.50    2.33    --  105.75 -94.00-150.00   94
 30  \w     84.00 128.00   0.50    2.33    --  105.75-140.00-154.00   88
 31  \w     54.00 100.00   0.50    2.33    --  105.75 -94.00-180.00   92
 32  \w     40.00  97.00   0.50    0.58    --   49.62-140.00-154.00  114
 33  \w     35.00 122.00   0.50    2.33    --  105.75-131.00 -38.99  174
 34  \w     39.00  64.00   0.50    2.33    --  105.75-125.00 -60.00   50
 35  \w     42.00  88.00   0.50    2.33    --  105.75 -94.00   0.00   92
 36  \w     33.00  69.00   0.50    2.33    --  105.75 -15.00  60.00   72
 37  \w     35.00  71.00   0.50    2.33    --  105.75 -30.00 120.00   72
 38  \w     54.00  86.00   0.50    2.33    --  105.75 -45.00 150.00   64
 39  \w     34.00  69.00   0.50    2.33    --  105.75 -94.00 150.00   70
 40  \w     40.00 116.00   0.50    2.33    --  105.75-125.00  90.00  152
 41  \w     36.00  72.00   0.50    2.33    --  105.75 -94.00 -30.00   72
 42  \w     33.00  82.00   0.50    2.33    --  105.75 -15.00 -60.00   98
 43  \w     41.00  82.00   0.50    2.33    --  105.75-125.00  60.00   82
 44  \w     34.00 120.00   0.50    2.33    --  105.75 -61.00 150.00  172
 45  \w     33.00  82.00   0.50    2.33    --  105.75 -15.00 150.00   98
 46  \w    -21.00  57.00   0.50    0.58    --   49.62 -38.00   0.00  156
 47  \w    -84.00 -59.00   0.50    2.33    --  -84.25 140.00 -95.00   50
 48  \w    -91.00 -64.00   0.50    0.58    --  -49.62 140.00 -95.00   54
 49  \w    -82.00 -52.00   0.50    2.33    --  -84.25 129.00  91.00   60
 50  \w    -93.00 -49.00   0.50    0.58    --  -49.62 129.00  91.00   88
 51  \w   -121.00 -43.00   0.50    0.58    --  -49.62 -38.00-150.00  156
 52  \w   -105.00 -61.00   0.50    0.58    --  -49.62-140.00-154.00   88
 53  \w   -116.00 -91.00   0.50    2.33    --  -84.25-140.00-154.00   50
 54  \w   -109.00 -77.00   0.50    0.58    --  -49.62-125.00-180.00   64
 55  \w   -115.00 -88.00   0.50    0.58    --  -49.62-125.00 -30.00   54
 56  \w   -117.00 -73.00   0.50    0.58    --  -49.62-129.00  18.00   88
 57  \w   -136.00-111.00   0.50    2.33    --  -84.25-129.00  18.00   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      0.0915261000
_diffrn_orient_matrix_UB_12      0.0606832000
_diffrn_orient_matrix_UB_13      -0.0443492000
_diffrn_orient_matrix_UB_21      -0.0536401000
_diffrn_orient_matrix_UB_22      0.0049680000
_diffrn_orient_matrix_UB_23      -0.0630135000
_diffrn_orient_matrix_UB_31      -0.0822598000
_diffrn_orient_matrix_UB_32      0.1117878000
_diffrn_orient_matrix_UB_33      0.0028090000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            52439
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.714
_diffrn_reflns_theta_min         3.652
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.192
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77574
_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            red-black
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_description       plate
_exptl_crystal_F_000             1223
_exptl_crystal_size_max          0.215
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.846
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.073
_refine_ls_extinction_coef       0.00113(19)
_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   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         12578
_refine_ls_number_restraints     160
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0564
_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^)+(0.1014P)^2^+1.1144P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1597
_refine_ls_wR_factor_ref         0.1662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10793
_reflns_number_total             12578
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04869_si_004.cif
_cod_data_source_block           neipn25
_cod_database_code               4128289
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         MgBrClO8C32H64FeC32H30
_shelx_estimated_absorpt_t_max   0.862
_shelx_estimated_absorpt_t_min   0.547
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Br1, Cl1}
3. Restrained distances
 Fe1-C26 \\sim Fe1-C26'
 with sigma of 0.01
 O3-C44 \\sim O3-C44' \\sim O4-C45 \\sim O4-C45'
 with sigma of 0.01
 C42-C43 \\sim C42-C43' \\sim C43-C44 \\sim C43'-C44' \\sim C45-C46 \\sim
C45'-C46' \\sim C46-C47 ~
 C46'-C47
 with sigma of 0.01
4. Restrained planarity
 C29, C32, C27, C28, C30, C31
 with sigma of 0.02
 C29', C32', C27', C28', C30', C31'
 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
O7 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C26) = Uanis(C26')
Uanis(C27) = Uanis(C27')
Uanis(C28) = Uanis(C28')
Uanis(C29) = Uanis(C29')
Uanis(C30) = Uanis(C30')
Uanis(C31) = Uanis(C31')
Uanis(C32) = Uanis(C32')
Uanis(Br1) = Uanis(Cl1)
Uanis(C45) = Uanis(C45')
Uanis(C46) = Uanis(C46')
Uanis(C43) = Uanis(C43')
Uanis(C44) = Uanis(C44')
Uanis(O7) = Uanis(O7')
Uanis(C57) = Uanis(C57')
Uanis(C58) = Uanis(C58')
Uanis(C59) = Uanis(C59')
Uanis(C60) = Uanis(C60')
Uanis(O8) = Uanis(O8')
Uanis(C61) = Uanis(C61')
Uanis(C62) = Uanis(C62')
Uanis(C63) = Uanis(C63')
Uanis(C64) = Uanis(C64')
6. Same fragment restrains
{C32, C31, C30, C29, C28, C27} sigma for 1-2: 0.02, 1-3: 0.04
as
{C27, C28, C29, C30, C31, C32}
{C25, C26, C27, C28, C29, C30, C31, C32} sigma for 1-2: 0.02, 1-3: 0.04
as
{C25', C26', C27', C28', C29', C30', C31', C32'}
{O7, C60, C59, C58, C57} sigma for 1-2: 0.02, 1-3: 0.04
as
{O7, C57, C58, C59, C60}
{O8, C64, C63, C62, C61} sigma for 1-2: 0.02, 1-3: 0.04
as
{O8, C61, C62, C63, C64}
{O7', C60', C59', C58', C57'} sigma for 1-2: 0.02, 1-3: 0.04
{O7, C57, C58, C59, C60} sigma for 1-2: 0.02, 1-3: 0.04
as
{O7', C57', C58', C59', C60'}
{O8, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
{O8', C64', C63', C62', C61'} sigma for 1-2: 0.02, 1-3: 0.04
as
{O8', C61', C62', C63', C64'}
7. Others
 Sof(C25')=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26')=Sof(H26')=Sof(C27')=
 Sof(C28')=Sof(H28')=Sof(C29')=Sof(H29')=Sof(C30')=Sof(H30')=Sof(C31')=
 Sof(H31')=Sof(C32')=Sof(H32')=1-FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(C28)=
 Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=
 Sof(H32)=FVAR(1)
 Sof(Cl1)=1-FVAR(2)
 Sof(Br1)=FVAR(2)
 Sof(H42C)=Sof(H42D)=Sof(C43')=Sof(H43C)=Sof(H43D)=Sof(C44')=Sof(H44C)=
 Sof(H44D)=1-FVAR(3)
 Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 FVAR(3)
 Sof(C45')=Sof(H45C)=Sof(H45D)=Sof(C46')=Sof(H46C)=Sof(H46D)=Sof(H47C)=
 Sof(H47D)=1-FVAR(4)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H47A)=Sof(H47B)=
 FVAR(4)
 Sof(O7')=Sof(C57')=Sof(H57C)=Sof(H57D)=Sof(C58')=Sof(H58C)=Sof(H58D)=
 Sof(C59')=Sof(H59C)=Sof(H59D)=Sof(C60')=Sof(H60C)=Sof(H60D)=1-FVAR(5)
 Sof(O7)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=
 Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=FVAR(5)
 Sof(O8')=Sof(C61')=Sof(H61C)=Sof(H61D)=Sof(C62')=Sof(H62C)=Sof(H62D)=
 Sof(C63')=Sof(H63C)=Sof(H63D)=Sof(C64')=Sof(H64C)=Sof(H64D)=1-FVAR(6)
 Sof(O8)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=
 Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=FVAR(6)
8.a Ternary CH refined with riding coordinates:
 C2(H2), C10(H10), C18(H18), C26(H26), C26'(H26')
8.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C9(H9A,H9B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B),
  C41(H41A,H41B), C42(H42A,H42B), C42(H42C,H42D), C43(H43A,H43B), C44(H44A,
 H44B), C43'(H43C,H43D), C44'(H44C,H44D), C45(H45A,H45B), C46(H46A,H46B),
 C45'(H45C,H45D), C46'(H46C,H46D), C47(H47A,H47B), C47(H47C,H47D), C48(H48A,
 H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B),
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B),
  C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,
 H62B), C63(H63A,H63B), C64(H64A,H64B), C57'(H57C,H57D), C58'(H58C,H58D),
 C59'(H59C,H59D), C60'(H60C,H60D), C61'(H61C,H61D), C62'(H62C,H62D), C63'(H63C,
 H63D), C64'(H64C,H64D)
8.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C28'(H28'), C29'(H29'),
 C30'(H30'), C31'(H31'), C32'(H32')
8.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C25'(H25D,H25E,H25F)
;
_shelx_res_checksum              28769
_shelx_hkl_checksum              49224
_olex2_submission_original_sample_id neipn25
_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 1.366
_oxdiff_exptl_absorpt_empirical_full_min 0.779