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_1576122
_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         'C22 H42 Fe O2 P4'
_chemical_formula_sum            'C22 H42 Fe O2 P4'
_chemical_formula_weight         518.28
_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   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2025-01-07
_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                 99.482(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1635(6)
_cell_length_b                   15.4314(11)
_cell_length_c                   18.7645(13)
_cell_measurement_reflns_used    8541
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.8940
_cell_measurement_theta_min      3.6960
_cell_volume                     2617.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.135a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.135a 64-bit (release 19-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.135a (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 2018/3 (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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     42.00 124.00   0.50    1.00    --   47.67  39.00  63.00  164
  2  \w   -124.00 -43.00   0.50    1.00    --  -48.55 -39.00 -91.00  162
  3  \w    -17.00  27.00   0.50    1.00    --  -48.55  39.00  63.00   88
  4  \w   -164.00 -83.00   0.50    4.00    --  -88.15 -39.00 -91.00  162
  5  \w   -163.00-131.00   0.50    4.00    --  -88.15 -39.00 -91.00   64
  6  \w    105.00 173.00   0.50    4.00    --  108.29  39.00  63.00  136
  7  \w    -42.00 -13.00   0.50    1.00    --    6.00 130.00 -97.41   58
  8  \w    -19.00   7.00   0.50    1.00    --   10.00  96.00 174.33   52
  9  \w     -7.00  18.00   0.50    1.00    --   14.00  83.00   9.60   50
 10  \w     22.00  47.00   0.50    1.00    --   34.00  67.00 106.80   50
 11  \w    -20.00   7.00   0.50    1.00    --   47.67 -39.00 -91.00   54
 12  \w     91.00 124.00   0.50    1.00    --   47.67  39.00  63.00   66
 13  \w   -143.00-111.00   0.50    4.00    --  -88.15 -77.00  30.00   64
 14  \w    -72.00 -29.00   0.50    4.00    --  -88.15  77.00-150.00   86
 15  \w    -46.00 -19.00   0.50    4.00    --  -88.15  61.00  30.00   54
 16  \w    -47.00 -22.00   0.50    4.00    --  -88.15  61.00   0.00   50
 17  \w    -45.00 -18.00   0.50    4.00    --  -88.15  61.00  60.00   54
 18  \w    -46.00 -17.00   0.50    4.00    --  -88.15  61.00 -90.00   58
 19  \w    -45.00 -16.00   0.50    4.00    --  -88.15  61.00-120.00   58
 20  \w    -46.00 -16.00   0.50    4.00    --  -88.15  61.00-180.00   60
 21  \w   -151.00-106.00   0.50    4.00    --  -88.15 -77.00-180.00   90
 22  \w    -43.00 -16.00   0.50    4.00    --  -88.15  61.00 150.00   54
 23  \w    116.00 150.00   0.50    4.00    --  108.29  45.00  90.00   68
 24  \w    111.00 146.00   0.50    4.00    --  108.29  77.00 -90.00   70
 25  \w     43.00  89.00   0.50    4.00    --  108.29 -95.00 150.00   92
 26  \w     99.00 126.00   0.50    4.00    --  108.29  61.00  90.00   54
 27  \w     92.00 131.00   0.50    4.00    --  108.29  15.00-120.00   78
 28  \w     50.00  77.00   0.50    4.00    --  108.29 -77.00 150.00   54
 29  \w     52.00  87.00   0.50    4.00    --  108.29 -95.00-180.00   70
 30  \w     60.00  87.00   0.50    4.00    --  108.29 -95.00-150.00   54
 31  \w     46.00  74.00   0.50    4.00    --  108.29 -77.00  60.00   56
 32  \w     95.00 138.00   0.50    4.00    --  108.29  15.00  60.00   86
 33  \w     39.00  68.00   0.50    4.00    --  108.29-125.00   0.00   58
 34  \w     44.00  71.00   0.50    4.00    --  108.29 -77.00 120.00   54
 35  \w    108.00 157.00   0.50    4.00    --  108.29  45.00-150.00   98
 36  \w     43.00  68.00   0.50    4.00    --  108.29 -77.00 -30.00   50
 37  \w     43.00  72.00   0.50    4.00    --  108.29 -77.00-150.00   58
 38  \w     96.00 148.00   0.50    4.00    --  108.29 125.00 120.00  104
 39  \w    111.00 176.00   0.50    4.00    --  108.29  45.00 120.00  130
 40  \w     43.00  68.00   0.50    4.00    --  108.29 -95.00  30.00   50
 41  \w     99.00 139.00   0.50    4.00    --  108.29  15.00  30.00   80
 42  \w     46.00  72.00   0.50    4.00    --  108.29 -95.00-120.00   52
 43  \w    100.00 137.00   0.50    4.00    --  108.29  61.00 150.00   74
 44  \w    140.00 167.00   0.50    4.00    --  108.29  30.00  90.00   54
 45  \w    110.00 137.00   0.50    4.00    --  108.29  30.00  90.00   54
 46  \w    138.00 165.00   0.50    4.00    --  108.29 125.00   0.00   54
 47  \w    106.00 139.00   0.50    4.00    --  108.29  15.00-180.00   66
 48  \w    116.00 145.00   0.50    4.00    --  108.29  77.00-150.00   58
 49  \w    100.00 127.00   0.50    4.00    --  108.29  61.00-180.00   54
 50  \w     45.00  70.00   0.50    4.00    --  108.29 -77.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1307096000
_diffrn_orient_matrix_UB_12      0.0479546000
_diffrn_orient_matrix_UB_13      -0.0244615000
_diffrn_orient_matrix_UB_21      0.0916764000
_diffrn_orient_matrix_UB_22      -0.0120665000
_diffrn_orient_matrix_UB_23      0.0758761000
_diffrn_orient_matrix_UB_31      0.0593967000
_diffrn_orient_matrix_UB_32      -0.0867433000
_diffrn_orient_matrix_UB_33      -0.0240408000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0929
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19769
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        50.433
_diffrn_reflns_theta_max         50.433
_diffrn_reflns_theta_min         3.729
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    7.051
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.675
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.135a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent dark orange'
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       plate
_exptl_crystal_F_000             1104
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of THF-d8 and pentane  by slow evaporation'
_exptl_crystal_size_max          0.077
_exptl_crystal_size_mid          0.047
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.145
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         2737
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0762
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0723P)^2^+16.9421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1989
_refine_ls_wR_factor_ref         0.2024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2446
_reflns_number_total             2737
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           15
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_original_cell_volume        2617.1(3)
_cod_database_code               1576122
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H42 O2 P4 Fe1 '
_chemical_oxdiff_usercomment     '@ 100 K JHPC313'
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.613
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C17(H17A,H17B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              32211
_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 313'
_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 2.686
_oxdiff_exptl_absorpt_empirical_full_min 0.508