Markovnikov-Selective, Activator-Free Iron-Catalyzed Vinylarene Hydroboration
MacNair, Alistair J.; Millet, Clément R. P.; Nichol, Gary S.; Ironmonger, Alan; Thomas, Stephen P.; ACS Catalysis 6 (2016) 7217–; doi:10.1021/acscatal.6b02281

data_4516712
_publ_section_title
;
 Markovnikov-Selective, Activator-Free Iron-Catalyzed Vinylarene
 Hydroboration
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              7217
_journal_paper_doi               10.1021/acscatal.6b02281
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C126 H138 Fe4 N12 O6, 2(F6 P), 4(C6 H6)'
_chemical_formula_sum            'C150 H162 F12 Fe4 N12 O6 P2'
_chemical_formula_weight         2742.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-25
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.7811(6)
_cell_length_b                   22.9453(6)
_cell_length_c                   13.3383(3)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      28.04
_cell_measurement_theta_min      2.51
_cell_volume                     6972.2(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       APEX2
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      120.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker SMART APEXII diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0140
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            321877
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.315
_diffrn_reflns_theta_min         2.507
_diffrn_source                   Mo
_diffrn_source_current           30
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.506
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0545 before and 0.0498 after correction.
The Ratio of minimum to maximum transmission is 0.8924.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             2872
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of THF, benzene and hexane by vapour diffusion'
_exptl_crystal_size_max          0.678
_exptl_crystal_size_mid          0.297
_exptl_crystal_size_min          0.132
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 7082 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0143(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     847
_refine_ls_number_reflns         17128
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0282
_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^)+(0.0452P)^2^+1.6346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0770
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                16121
_reflns_number_total             17128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b02281_si_006.cif
_cod_data_source_block           se16004
_cod_database_code               4516712
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.725
_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. Same fragment restrains
{C111, C112, C113, C114, C115, C116} sigma for 1-2: 0.02, 1-3: 0.02
as
{C101, C102, C103, C104, C105, C106}
3.a Ternary CH refined with riding coordinates:
 C6(H6), C36(H36), C66(H66)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C37(H37A,H37B), C39(H39A,H39B), C67(H67A,H67B),
 C69(H69A,H69B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C18(H18),
 C20(H20), C33(H33), C34(H34), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C48(H48), C50(H50), C63(H63), C64(H64), C71(H71), C72(H72), C73(H73),
 C74(H74), C75(H75), C78(H78), C80(H80), C101(H101), C102(H102), C103(H103),
 C104(H104), C105(H105), C106(H106), C111(H111), C112(H112), C113(H113),
 C114(H114), C115(H115), C116(H116)
3.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C52(H52A,H52B,
 H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C82(H82A,H82B,H82C), C83(H83A,
 H83B,H83C), C84(H84A,H84B,H84C)
;
_shelx_res_checksum              86266
_shelx_hkl_checksum              19226
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-04-22
_olex2_date_sample_submission    2016-04-19
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id AJM454-4
_olex2_submission_special_instructions 'No special instructions were received'