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_1567464
_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         'C16 H38 Fe O P4'
_chemical_formula_sum            'C16 H38 Fe O P4'
_chemical_formula_weight         426.19
_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             2022-01-20
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-16 deposited with the CCDC.	2022-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.957(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.6983(3)
_cell_length_b                   17.3967(3)
_cell_length_c                   17.9529(4)
_cell_measurement_reflns_used    34876
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      31.1810
_cell_measurement_theta_min      3.6860
_cell_volume                     4341.61(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.923
_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    -62.00  46.00   1.00    7.50    --   14.65 -23.00 135.00  108
  2  \w    -17.00  92.00   1.00    7.50    --   14.65  23.00 -59.00  109
  3  \w    -44.00  21.00   1.00    7.50    --  -12.93  77.00  30.00   65
  4  \w    -42.00  18.00   1.00    7.50    --  -12.93 -77.00  90.00   60
  5  \w    -42.00  18.00   1.00    7.50    --  -12.93 -77.00 -30.00   60
  6  \w    -42.00  46.00   1.00    7.50    --   14.65 -77.00  90.00   88
  7  \w    -56.00  41.00   1.00    7.50    --   14.65 -57.00-150.00   97
  8  \w    -12.00  85.00   1.00    7.50    --   14.65  57.00-150.00   97
  9  \w    -15.00  55.00   1.00    7.50    --   14.65 -99.00 -60.00   70
 10  \w    -44.00  13.00   1.00    7.50    --  -12.93  77.00 -30.00   57
 11  \w    -42.00  18.00   1.00    7.50    --  -12.93 -77.00  30.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0485970000
_diffrn_orient_matrix_UB_12      0.0099319000
_diffrn_orient_matrix_UB_13      -0.0201886000
_diffrn_orient_matrix_UB_21      -0.0071084000
_diffrn_orient_matrix_UB_22      0.0076727000
_diffrn_orient_matrix_UB_23      0.0365225000
_diffrn_orient_matrix_UB_31      0.0138382000
_diffrn_orient_matrix_UB_32      0.0387885000
_diffrn_orient_matrix_UB_33      -0.0020470000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            114056
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.923
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.324
_diffrn_reflns_theta_min         3.156
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.990
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86380
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent dark yellow'
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1824
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of pentane and THF  by slow cooling'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.671
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     727
_refine_ls_number_reflns         13141
_refine_ls_number_restraints     153
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0289P)^2^+1.7633P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0689
_refine_ls_wR_factor_ref         0.0754
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10498
_reflns_number_total             13141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03802a2.cif
_cod_data_source_block           se22002
_cod_database_code               1567464
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H37 B1 Fe1 O2 P4'
_chemical_oxdiff_usercomment     '@ 120 K LAB302'
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.736
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Fe51-C51 \\sim Fe51-C51A
 with sigma of 0.02
 O51-C51 \\sim O51A-C51A
 with sigma of 0.02
 O51-C54 \\sim O51A-C54A
 with sigma of 0.02
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 C51-C54 \\sim C51A-C54A
 with sigma of 0.04
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C51-C53 \\sim C51A-C53A
 with sigma of 0.04
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 Fe51-O51 \\sim Fe51-O51A
 with sigma of 0.04
 Fe51-C52 \\sim Fe51-C52A
 with sigma of 0.04
 O51-C52 \\sim O51A-C52A
 with sigma of 0.04
 O51-C53 \\sim O51A-C53A
 with sigma of 0.04
3. Rigid bond restraints
 O51, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O51A, C51A, C52A, C53A, C54A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O51A \\sim C51A \\sim C52A \\sim C53A \\sim C54A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O51 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O51A, C51A, C52A, C53A, C54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O51, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O51A)=Sof(C51A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53C)=Sof(H53D)=
 Sof(C54A)=Sof(H54C)=Sof(H54D)=1-FVAR(1)
 Sof(O51)=Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=
 Sof(H54A)=Sof(H54B)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C53A(H53C,H53D), C54(H54A,H54B), C54A(H54C,H54D)
7.b Aromatic/amide H refined with riding coordinates:
 C52(H52), C52A(H52A)
;
_shelx_res_checksum              5489
_shelx_hkl_checksum              28369
_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 LAB302
_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 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.812