Molecular-level insight into the multiple mechanistic pathways in iron-catalysed alkene dimerisation.
Cockcroft, Joseph H. P.; Flook, Annabel; Boaler, Patrick J.; Nichol, Gary S.; Holt, Jarle; Smit, Joost; Garden, Jennifer A.; Thomas, Stephen P.; Chemical science 16 (2025) 22394–22406; doi:10.1039/d5sc07490h

data_1576123
_publ_section_title
;
 Molecular-level insight into the multiple mechanistic pathways in
 iron-catalysed alkene dimerisation.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22394
_journal_page_last               22406
_journal_paper_doi               10.1039/d5sc07490h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C16 H38 Fe O2 P4'
_chemical_formula_sum            'C16 H38 Fe O2 P4'
_chemical_formula_weight         442.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-11
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-21 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.007(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5261(4)
_cell_length_b                   8.9654(3)
_cell_length_c                   17.4240(5)
_cell_measurement_reflns_used    9827
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.171
_cell_measurement_theta_min      2.555
_cell_volume                     2269.17(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       APEX5
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0495
_diffrn_reflns_av_unetI/netI     0.0157
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            133142
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.298
_diffrn_reflns_theta_min         2.272
_diffrn_source                   ImuS-Mo
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.952
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6771
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0878 before and 0.0646 after correction.
The Ratio of minimum to maximum transmission is 0.9080.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_recrystallization_method
'The material was recrystallised from pentane by slow evaporation'
_exptl_crystal_size_max          0.472
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.279
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.453
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         5639
_refine_ls_number_restraints     956
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0432P)^2^+1.9669P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0949
_refine_ls_wR_factor_ref         0.0974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5395
_reflns_number_total             5639
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           16
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_database_code               1576123
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.662
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5368(13)
 0.4632(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All Fe(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{P3, P4A}
4. Restrained distances
 Fe1-P1 \\sim Fe1-P4A
 with sigma of 0.02
 P4-C16 \\sim P1A-C8A
 with sigma of 0.02
 Fe1-C16 \\sim Fe1-C8A
 with sigma of 0.04
 Fe1-P3 \\sim Fe1-P2A
 with sigma of 0.02
 Fe1-P4 \\sim Fe1-P1A
 with sigma of 0.02
 C12-C16 \\sim C5A-C8A
 with sigma of 0.04
 Fe1-P2 \\sim Fe1-P3A
 with sigma of 0.02
 C15-C16 \\sim C7A-C8A
 with sigma of 0.04
 P1-C7 \\sim P4A-C15A
 with sigma of 0.02
 P1-C8 \\sim P4A-C16A
 with sigma of 0.02
 P1-C5 \\sim P4A-C12A
 with sigma of 0.02
 P3-C11 \\sim P2A-C6A
 with sigma of 0.02
 P3-C13 \\sim P2A-C9A
 with sigma of 0.02
 P3-C14 \\sim P2A-C10A
 with sigma of 0.02
 P4-C12 \\sim P1A-C5A
 with sigma of 0.02
 P4-C15 \\sim P1A-C7A
 with sigma of 0.02
 P2-C9 \\sim P3A-C13A
 with sigma of 0.02
 P2-C10 \\sim P3A-C14A
 with sigma of 0.02
 P2-C6 \\sim P3A-C11A
 with sigma of 0.02
 C12-C11 \\sim C5A-C6A
 with sigma of 0.02
 C5-C6 \\sim C12A-C11A
 with sigma of 0.02
 Fe1-C7 \\sim Fe1-C15A
 with sigma of 0.04
 Fe1-C8 \\sim Fe1-C16A
 with sigma of 0.04
 Fe1-C9 \\sim Fe1-C13A
 with sigma of 0.04
 Fe1-C12 \\sim Fe1-C5A
 with sigma of 0.04
 Fe1-C11 \\sim Fe1-C6A
 with sigma of 0.04
 Fe1-C15 \\sim Fe1-C7A
 with sigma of 0.04
 Fe1-C5 \\sim Fe1-C12A
 with sigma of 0.04
 Fe1-C13 \\sim Fe1-C9A
 with sigma of 0.04
 Fe1-C14 \\sim Fe1-C10A
 with sigma of 0.04
 Fe1-C10 \\sim Fe1-C14A
 with sigma of 0.04
 Fe1-C6 \\sim Fe1-C11A
 with sigma of 0.04
 P1-C6 \\sim P4A-C11A
 with sigma of 0.04
 P3-C12 \\sim P2A-C5A
 with sigma of 0.04
 P4-C11 \\sim P1A-C6A
 with sigma of 0.04
 P2-C5 \\sim P3A-C12A
 with sigma of 0.04
 C7-C8 \\sim C15A-C16A
 with sigma of 0.04
 C7-C5 \\sim C15A-C12A
 with sigma of 0.04
 C8-C5 \\sim C16A-C12A
 with sigma of 0.04
 C9-C10 \\sim C13A-C14A
 with sigma of 0.04
 C9-C6 \\sim C13A-C11A
 with sigma of 0.04
 C12-C15 \\sim C5A-C7A
 with sigma of 0.04
 C11-C13 \\sim C6A-C9A
 with sigma of 0.04
 C11-C14 \\sim C6A-C10A
 with sigma of 0.04
 C13-C14 \\sim C9A-C10A
 with sigma of 0.04
 C10-C6 \\sim C14A-C11A
 with sigma of 0.04
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
Uanis(P3) = Uanis(P4A)
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7. Others
 Sof(O1A)=Sof(O2A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=1-FVAR(1)
 Sof(O1)=Sof(O2)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4A)=
 Sof(H4B)=Sof(H4C)=FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=
 Sof(H6AA)=Sof(H6AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=
 Sof(H12D)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(P1)=Sof(P2)=Sof(P3)=Sof(P4)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=
 Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(2)
8.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C5A(H5AA,H5AB), C6(H6A,H6B), C6A(H6AA,H6AB), C11(H11A,H11B),
 C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,H12D)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC), C7(H7A,H7B,H7C), C7A(H7AA,H7AB,H7AC),
 C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC), C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC),
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F), C13(H13A,H13B,H13C), C13A(H13D,H13E,
 H13F), C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C),
 C15A(H15D,H15E,H15F), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F)
8.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C2A(H2A), C3(H3), C3A(H3A)
;
_shelx_res_checksum              53530
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mitegen tip in Paratone oil.'
_olex2_submission_original_sample_id 'JHPC 286 mystery crystal'
_olex2_submission_special_instructions 'No special instructions were received'