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_1576125
_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         'C30 H80 Fe2 P10'
_chemical_formula_sum            'C30 H80 Fe2 P10'
_chemical_formula_weight         862.34
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-11-24
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-22 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.480(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3811(4)
_cell_length_b                   13.8289(3)
_cell_length_c                   19.7524(5)
_cell_measurement_reflns_used    13148
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.5400
_cell_measurement_theta_min      2.8300
_cell_volume                     4474.41(18)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -71.00 -19.00   0.50  120.00    --   -0.60 -19.00   0.00  104
  2  \w     19.00  70.00   0.50  120.00    --   -0.60  19.00   0.00  102
  3  \w    -59.00   1.00   0.50  120.00    --   -0.60 -57.00  60.00  120
  4  \w    -72.00  -5.00   0.50  120.00    --   -0.60 -38.00 150.00  134
  5  \w    -71.00 -28.00   0.50  120.00    --   -0.60 -19.00-150.00   86
  6  \w    -71.00 -19.00   0.50  120.00    --   -0.60 -19.00 -60.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0269760000
_diffrn_orient_matrix_UB_12      -0.0044633000
_diffrn_orient_matrix_UB_13      -0.0280999000
_diffrn_orient_matrix_UB_21      0.0296035000
_diffrn_orient_matrix_UB_22      -0.0278739000
_diffrn_orient_matrix_UB_23      -0.0172748000
_diffrn_orient_matrix_UB_31      -0.0164606000
_diffrn_orient_matrix_UB_32      -0.0428321000
_diffrn_orient_matrix_UB_33      0.0141857000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            56573
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.815
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.026
_exptl_absorpt_correction_T_max  0.94986
_exptl_absorpt_correction_T_min  0.94986
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent pale orange'
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             1848
_exptl_crystal_recrystallization_method
'The material was recrystallised from d8-THF by spontaneous crystallization from  365 nm photoirradiation at room temperature over 24 hours'
_exptl_crystal_size_max          0.095
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.041
_exptl_crystal_size_rad          0.032
_refine_diff_density_max         3.189
_refine_diff_density_min         -0.667
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     585
_refine_ls_number_reflns         9144
_refine_ls_number_restraints     1321
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1019
_refine_ls_R_factor_gt           0.0816
_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^)+(0.0983P)^2^+19.3870P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1990
_refine_ls_wR_factor_ref         0.2123
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7075
_reflns_number_total             9144
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           26
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_original_cell_volume        4474.39(19)
_cod_database_code               1576125
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C28 H72 P10 Fe2 '
_chemical_oxdiff_usercomment     '@ 100 K JHPC 295'
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.909
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 P3-C7 \\sim P3-C7A
 with sigma of 0.02
 C13-C14 \\sim C13-C14A
 with sigma of 0.02
 C8-C7 \\sim C8-C7A
 with sigma of 0.02
 P2-C2 \\sim P2-C2A
 with sigma of 0.02
 C1-C2 \\sim C1-C2A
 with sigma of 0.02
 C2-P2A \\sim C2A-P2A
 with sigma of 0.02
 P3-C7A \\sim P3-C7
 with sigma of 0.02
 C8-C7A \\sim C8-C7
 with sigma of 0.02
 C14A-C13 \\sim C14-C13
 with sigma of 0.02
 P6-C14 \\sim P6-C14A
 with sigma of 0.02
 P1A-C4 \\sim P1-C4
 with sigma of 0.02
 P1A-C1 \\sim P1-C1
 with sigma of 0.02
 C2A-C1 \\sim C2-C1
 with sigma of 0.02
 P2A-C2A \\sim P2-C2
 with sigma of 0.02
 P2A-C5 \\sim P2-C5
 with sigma of 0.02
 P2A-C6A \\sim P2-C6
 with sigma of 0.02
 Fe2A-P7A \\sim Fe2-P10 \\sim Fe2A-P10A \\sim Fe2-P9 \\sim Fe2A-P9A \\sim
Fe2-P8 \\sim Fe2A-P8A \\sim Fe2-P7
 with sigma of 0.02
 P7A-C19A \\sim P8A-C20A \\sim P7-C19 \\sim P8-C20 \\sim P9A-C25A \\sim
P10A-C26A \\sim P9-C25 \\sim P10-C26
 with sigma of 0.02
 P10-C29 \\sim P7A-C21A \\sim P10-C30 \\sim P7A-C22A \\sim P7-C21 \\sim P7-C22
\\sim P8A-C23A \\sim P8A-
 C24A \\sim P8-C24 \\sim P8-C23 \\sim P9A-C28A \\sim P9A-C27A \\sim P9-C27
\\sim P10A-C30A \\sim P9-C28 ~
 P10A-C29A
 with sigma of 0.02
 C20A-C19A \\sim C20-C19 \\sim C26A-C25A \\sim C26-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C7A) = Uanis(C7)
Uanis(Fe2) = Uanis(Fe2A)
Uanis(P9) = Uanis(P10A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=1-FVAR(1)
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=FVAR(1)
 Sof(P7A)=Sof(P8A)=Sof(P9A)=Sof(P10A)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=
 Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=
 Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=
 Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(H25C)=Sof(H25D)=
 Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(P7)=Sof(P8)=Sof(P9)=Sof(P10)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 FVAR(2)
 Sof(H1BC)=Sof(H1BD)=Sof(H3BD)=Sof(H3BE)=Sof(H3BF)=Sof(H4BD)=Sof(H4BE)=
 Sof(H4BF)=Sof(H5BD)=Sof(H5BE)=Sof(H5BF)=Sof(H8BC)=Sof(H8BD)=Sof(Fe2A)=Sof(P1A)=
 Sof(P2A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-
 FVAR(3)
 Sof(H1AA)=Sof(H1AB)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(H8AA)=Sof(H8AB)=Sof(Fe2)=Sof(P1)=
 Sof(P2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(3)
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=1-FVAR(4)
 Sof(C7)=Sof(H7A)=Sof(H7B)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD), C8(H8AA,H8AB), C8(H8BC,H8BD), C13(H13A,H13B),
 C13(H13C,H13D), C2(H2A,H2B), C7(H7A,H7B), C14(H14A,H14B), C19(H19A,H19B),
 C20(H20A,H20B), C25(H25A,H25B), C26(H26A,H26B), C2A(H2AA,H2AB), C7A(H7AA,H7AB),
  C14A(H14C,H14D), C19A(H19C,H19D), C20A(H20C,H20D), C25A(H25C,H25D), C26A(H26C,
 H26D)
6.b Me refined with riding coordinates:
 C3(H3AA,H3AB,H3AC), C3(H3BD,H3BE,H3BF), C4(H4AA,H4AB,H4AC), C4(H4BD,H4BE,
 H4BF), C5(H5AA,H5AB,H5AC), C5(H5BD,H5BE,H5BF), C6(H6A,H6B,H6C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C6A(H6AA,H6AB,H6AC), C21A(H21D,H21E,H21F), C22A(H22D,H22E,H22F), C28A(H28D,
 H28E,H28F)
6.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C27A(H27D,H27E,H27F),
 C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
;
_shelx_res_checksum              3976
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 1000'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id 'JHPC 295 '
_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 2.339
_oxdiff_exptl_absorpt_empirical_full_min 0.712