Iron-catalysed Alkene and Heteroarene H/D Exchange by Reversible Protonation of Iron-hydride Intermediates
Britton, Luke; Docherty, Jamie; Sklyaruk, Jan; Cooney, Jessica; Nichol, Gary Stephen; Dominey, Andrew; Thomas, Stephen P.; Chemical Science  (2022) –; doi:10.1039/D2SC03802A

data_1567462
_publ_section_title
;
 Iron-catalysed Alkene and Heteroarene H/D Exchange by Reversible
 Protonation of Iron-hydride Intermediates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC03802A
_journal_year                    2022
_chemical_formula_moiety         'C20 H42 Fe N4 O2 P4'
_chemical_formula_sum            'C20 H42 Fe N4 O2 P4'
_chemical_formula_weight         550.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-10
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2021-03-26 deposited with the CCDC.	2022-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.861(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4604(6)
_cell_length_b                   17.5579(11)
_cell_length_c                   14.6107(9)
_cell_measurement_reflns_used    9509
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      35.31
_cell_measurement_theta_min      2.70
_cell_volume                     2682.0(3)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0136
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            241200
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.598
_diffrn_reflns_theta_min         2.267
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.7470
_exptl_absorpt_correction_T_min  0.6628
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1129 before and 0.0479 after correction.
The Ratio of minimum to maximum transmission is 0.8873.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_recrystallization_method
'The material was recrystallised from pentane by slow cooling'
_exptl_crystal_size_max          0.498
_exptl_crystal_size_mid          0.368
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.196
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     429
_refine_ls_number_reflns         11736
_refine_ls_number_restraints     262
_refine_ls_restrained_S_all      1.193
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0155P)^2^+2.6678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0911
_refine_ls_wR_factor_ref         0.0932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10664
_reflns_number_total             11736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03802a2.cif
_cod_data_source_block           se20006
_cod_database_code               1567462
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.684
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C3, C4A}
3. Restrained distances
 Fe1-P1A \\sim Fe1-P1
 with sigma of 0.02
 P2A-C6A \\sim P2-C6
 with sigma of 0.02
 P3-C9A \\sim P3-C9
 with sigma of 0.02
 Fe1-P2A \\sim Fe1-P2
 with sigma of 0.02
 P3-C7A \\sim P3-C7
 with sigma of 0.02
 P1A-C1A \\sim P1-C1
 with sigma of 0.02
 P4A-C11A \\sim P4-C11
 with sigma of 0.02
 C2A-C1A \\sim C2-C1
 with sigma of 0.02
 P2A-C2A \\sim P2-C2
 with sigma of 0.02
 P4A-C8A \\sim P4-C8
 with sigma of 0.02
 P1A-C3A \\sim P1-C3
 with sigma of 0.02
 P3-C10A \\sim P3-C10
 with sigma of 0.02
 P1A-C4A \\sim P1-C4
 with sigma of 0.02
 C8A-C7A \\sim C8-C7
 with sigma of 0.02
 P2A-C5A \\sim P2-C5
 with sigma of 0.02
 P4A-C12A \\sim P4-C12
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(C4A)
5. Rigid body (RIGU) restrains
 Fe1, P1A, P2A, P3, P4A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A,
 C11A, C12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Fe1, P1, P2, P3, P4, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(P1A)=Sof(P2A)=Sof(P4A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=
 Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=
 Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=1-FVAR(1)
 Sof(P1)=Sof(P2)=Sof(P4)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB), C2(H2A,H2B), C2A(H2AA,H2AB), C7(H7A,H7B),
 C7A(H7AA,H7AB), C8(H8A,H8B), C8A(H8AA,H8AB)
7.b Me refined with riding coordinates:
 C4A(H4AA,H4AB,H4AC)
7.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C3A(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C5A(H5AA,H5AB,H5AC), C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC), C9(H9A,H9B,H9C),
 C9A(H9AA,H9AB,H9AC), C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F), C11(H11A,H11B,
 H11C), C11A(H11D,H11E,H11F), C12(H12A,H12B,H12C), C12A(H12D,H12E,H12F),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              30454
_shelx_hkl_checksum              71418
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id JD12.021
_olex2_submission_special_instructions 'No special instructions were received'