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_1576124
_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         '2(C52 H48 Fe P4), 2.5(C5 H12)'
_chemical_formula_sum            'C116.5 H126 Fe2 P8'
_chemical_formula_weight         1885.63
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2024-08-06
_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                88.129(3)
_cell_angle_beta                 86.550(3)
_cell_angle_gamma                87.443(3)
_cell_formula_units_Z            2
_cell_length_a                   11.0746(9)
_cell_length_b                   20.0081(17)
_cell_length_c                   22.2287(19)
_cell_measurement_reflns_used    9895
_cell_measurement_temperature    100.10
_cell_measurement_theta_max      36.68
_cell_measurement_theta_min      2.53
_cell_volume                     4909.4(7)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.10
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            671176
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.171
_diffrn_reflns_theta_min         2.211
_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    0.476
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0992 before and 0.0566 after correction.
The Ratio of minimum to maximum transmission is 0.9140.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             1994
_exptl_crystal_recrystallization_method
'The material was recrystallised from hot methanol by slow cooling'
_exptl_crystal_size_max          0.338
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.845
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1222
_refine_ls_number_reflns         37409
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0300
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0377P)^2^+2.1190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0820
_reflns_Friedel_coverage         0.000
_reflns_number_gt                33176
_reflns_number_total             37409
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07490h2.cif
_cod_data_source_block           30
_cod_depositor_comments
'Adding full bibliography for 1576122--1576127.cif.'
_cod_original_formula_sum        'C116.50 H126 Fe2 P8'
_cod_database_code               1576124
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.856
_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. Same fragment restrains
{C115, C116, C117, C118, C119} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C15A, C16A, C17A, C18A, C19A}
3. Others
 Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16A)=Sof(H16B)=
 Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(C19A)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(1)
 Sof(C115)=Sof(H11M)=Sof(H11N)=Sof(H11O)=Sof(C116)=Sof(H11P)=Sof(H11Q)=
 Sof(C117)=Sof(H11R)=Sof(H11S)=Sof(C118)=Sof(H11T)=Sof(H11U)=Sof(C119)=
 Sof(H11V)=Sof(H11W)=Sof(H11X)=FVAR(1)
 Fixed Sof: C110(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C111(0.5) H11D(0.5)
 H11E(0.5) C112(0.5) H11F(0.5) H11G(0.5) C113(0.5) H11H(0.5) H11I(0.5)
 C114(0.5) H11J(0.5) H11K(0.5) H11L(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C27(H27A,H27B), C28(H28A,H28B), C53(H53A,H53B),
 C54(H54A,H54B), C79(H79A,H79B), C80(H80A,H80B), C16A(H16A,H16B), C17A(H17A,
 H17B), C18A(H18A,H18B), C106(H10D,H10E), C107(H10F,H10G), C108(H10H,H10I),
 C111(H11D,H11E), C112(H11F,H11G), C113(H11H,H11I), C116(H11P,H11Q), C117(H11R,
 H11S), C118(H11T,H11U)
4.b Me refined with riding coordinates:
 C15A(H15A,H15B,H15C), C19A(H19A,H19B,H19C)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
  C24(H24), C25(H25), C26(H26), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51),
 C52(H52), C56(H56), C57(H57), C58(H58), C59(H59), C62(H62), C63(H63), C64(H64),
  C65(H65), C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72),
 C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C82(H82), C83(H83), C84(H84),
  C85(H85), C86(H86), C88(H88), C89(H89), C90(H90), C91(H91), C92(H92),
 C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C100(H100), C101(H101),
 C102(H102), C103(H103), C104(H104)
4.d Idealised Me refined as rotating group:
 C105(H10A,H10B,H10C), C109(H10J,H10K,H10L), C110(H11A,H11B,H11C), C114(H11J,
 H11K,H11L), C115(H11M,H11N,H11O), C119(H11V,H11W,H11X)
;
_shelx_res_checksum              95227
_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 'JHPC 268 Tol'
_olex2_submission_special_instructions 'No special instructions were received'