Direct metathesis of carbon–carbon σ-bonds at a versatile macrocycle-supported diiron platform
Liu, Tianchang; Gonder, Jared E.; Murphy, Ryan P.; Bacon, Alexandra M.; Gau, Michael R.; Tomson, Neil C.; Chemical Science  (2026) –; doi:10.1039/D5SC10054B

data_1576581
_publ_section_title
;
 Direct metathesis of carbon-carbon <i>&#x3c3;</i>-bonds at a versatile
 macrocycle-supported diiron platform.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              7203
_journal_page_last               7210
_journal_paper_doi               10.1039/d5sc10054b
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety
'C76 H81 Fe2 N6 P2, C32 H12 B F24, 1.5(C4 H10 O)'
_chemical_formula_sum            'C114 H108 B F24 Fe2 N6 O1.5 P2'
_chemical_formula_weight         2226.51
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-08-02 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                66.9760(10)
_cell_angle_beta                 76.1840(10)
_cell_angle_gamma                76.6860(10)
_cell_formula_units_Z            2
_cell_length_a                   14.09570(10)
_cell_length_b                   20.1889(2)
_cell_length_c                   21.1235(2)
_cell_measurement_reflns_used    38844
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.2880
_cell_measurement_theta_min      2.6560
_cell_volume                     5308.95(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-6000HE
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.978
_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   -120.00 -34.00   0.50    7.00    --  -47.51 -44.00 -99.00  172
  2  \w    -53.00  25.00   0.50    7.00    --  -47.51  44.00  51.00  156
  3  \w    -25.00  47.00   0.50    7.00    --   47.51 -44.00 -99.00  144
  4  \w     34.00 120.00   0.50    7.00    --   47.51  44.00  51.00  172
  5  \w   -163.00 -76.00   0.50    7.00    --  -90.00 -44.00 -99.00  174
  6  \w    -53.00 -17.00   0.50    7.00    --  -90.00  44.00  51.00   72
  7  \w     98.00 178.00   0.50    7.00    --  112.88  44.00  51.00  160
  8  \w    -30.00  29.00   0.50    7.00    --  -47.51  19.00   0.00  118
  9  \w    -63.00 -21.00   0.50    7.00    --  -47.51  77.00 120.00   84
 10  \w    -25.00  29.00   0.50    7.00    --  -47.51  19.00  60.00  108
 11  \w    -15.00  12.00   0.50    7.00    --  -47.51  77.00 -60.00   54
 12  \w    -28.00  17.00   0.50    7.00    --   47.51 -19.00 120.00   90
 13  \w    -17.00  23.00   0.50    7.00    --   47.51 -19.00 150.00   80
 14  \w    -52.00 -17.00   0.50    7.00    --  -90.00  61.00-180.00   70
 15  \w   -101.00 -63.00   0.50    7.00    --  -90.00  80.00 115.61   76
 16  \w    -52.00 -17.00   0.50    7.00    --  -90.00  45.00-120.00   70
 17  \w   -107.00 -25.00   0.50    7.00    --  -90.00  77.00-150.00  164
 18  \w    -53.00 -20.00   0.50    7.00    --  -90.00  45.00  60.00   66
 19  \w    -49.00 -23.00   0.50    7.00    --  -90.00  45.00 150.00   52
 20  \w    -54.00 -18.00   0.50    7.00    --  -90.00  45.00 -60.00   72
 21  \w    -72.00 -34.00   0.50    7.00    --  -90.00  61.00 -90.00   76
 22  \w    -52.00 -18.00   0.50    7.00    --  -90.00  45.00 -30.00   68
 23  \w    102.00 178.00   0.50    7.00    --  112.88  45.00   0.00  152
 24  \w     48.00  74.00   0.50    7.00    --  112.88 -77.00-120.00   52
 25  \w     48.00  74.00   0.50    7.00    --  112.88 -77.00   0.00   52
 26  \w     39.00  64.00   0.50    7.00    --  112.88 -61.00 120.00   50
 27  \w    101.00 177.00   0.50    7.00    --  112.88  15.00 120.00  152
 28  \w    100.00 138.00   0.50    7.00    --  112.88 -80.00-166.01   76
 29  \w     39.00  79.00   0.50    7.00    --  112.88 -77.00  60.00   80
 30  \w     42.00  67.00   0.50    7.00    --  112.88 -61.00 150.00   50
 31  \w     39.00  71.00   0.50    7.00    --  112.88 -77.00 150.00   64
 32  \w     40.00  67.00   0.50    7.00    --  112.88 -61.00 -60.00   54
 33  \w     58.00 107.00   0.50    7.00    --  112.88 -78.00 -17.22   98
 34  \w     73.00  99.00   0.50    7.00    --  112.88 -77.00-150.00   52
 35  \w     39.00 106.00   0.50    7.00    --  112.88 -80.00  78.46  134
 36  \w     41.00  68.00   0.50    7.00    --  112.88 -61.00  90.00   54
 37  \w     39.00  90.00   0.50    7.00    --  112.88 -80.00-166.01  102
 38  \w     39.00  66.00   0.50    7.00    --  112.88 -61.00-150.00   54
 39  \w     77.00 138.00   0.50    7.00    --  112.88 -80.00 -73.97  122
 40  \w     40.00  67.00   0.50    7.00    --  112.88 -61.00-120.00   54
 41  \w     70.00  96.00   0.50    7.00    --  112.88 -80.00 -89.76   52
 42  \w     69.00 136.00   0.50    7.00    --  112.88 -80.00 170.69  134
 43  \w     95.00 121.00   0.50    7.00    --  112.88 -80.00  97.37   52
 44  \w    110.00 173.00   0.50    7.00    --  112.88  61.00 -30.00  126
 45  \w     75.00 110.00   0.50    7.00    --  112.88 -79.00  46.91   70
 46  \w     98.00 178.00   0.50    7.00    --  112.88  15.00 150.00  160
 47  \w     39.00  89.00   0.50    7.00    --  112.88 -77.00 -60.00  100
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0532523000
_diffrn_orient_matrix_UB_12      0.0512751000
_diffrn_orient_matrix_UB_13      0.0400212000
_diffrn_orient_matrix_UB_21      0.0947401000
_diffrn_orient_matrix_UB_22      0.0339025000
_diffrn_orient_matrix_UB_23      -0.0177724000
_diffrn_orient_matrix_UB_31      -0.0340606000
_diffrn_orient_matrix_UB_32      0.0571058000
_diffrn_orient_matrix_UB_33      -0.0673804000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            81595
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.501
_diffrn_reflns_theta_min         2.675
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.299
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66480
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       plate
_exptl_crystal_F_000             2298
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.532
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1562
_refine_ls_number_reflns         21228
_refine_ls_number_restraints     357
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0616P)^2^+3.1039P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18405
_reflns_number_total             21228
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc10054b2.cif
_cod_data_source_block           30015_Fe2CCPh+
_cod_depositor_comments
'Adding full bibliography for 1576580--1576582.cif.'
_cod_original_formula_sum        'C114 H108 B F24 Fe2 N6 O1.50 P2'
_cod_database_code               1576581
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.470
_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. Restrained distances
 F1*-C84 = F1-C84 = F3*-C84 = F3-C84 = F2*-C84 = F2-C84
 1.35 with sigma of 0.01
 F11*-C92 = F11-C92 = F12*-C92 = F12-C92 = F10-C92 = F10*-C92
 1.35 with sigma of 0.01
 F17-C100 = F17*-C100 = F18*-C100
 1.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O1 \\sim C109 \\sim C110 \\sim C111 \\sim C112: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
F23* \\sim F23 \\sim F22* \\sim F22 \\sim F24* \\sim F24: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim O3 \\sim C117 \\sim C118
\\sim C119 \\sim C120: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F4 \\sim F6* \\sim F5 \\sim F5* \\sim F6 \\sim F4*: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
F16 \\sim F17* \\sim F17 \\sim F18* \\sim F18: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
F11 \\sim F12* \\sim F12 \\sim F10* \\sim F10 \\sim F11*: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
F1 \\sim F3* \\sim F3 \\sim F2* \\sim F2 \\sim F1*: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
F14 \\sim F14* \\sim F15 \\sim F15* \\sim F13: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(F22*)=Sof(F23*)=Sof(F24*)=1-FVAR(1)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(F4*)=Sof(F5*)=Sof(F6*)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(F17*)=Sof(F18*)=1-FVAR(3)
 Sof(F17)=Sof(F18)=FVAR(3)
 Sof(F10*)=Sof(F11*)=Sof(F12*)=1-FVAR(4)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(4)
 Sof(F1*)=Sof(F2*)=Sof(F3*)=1-FVAR(5)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(5)
 Sof(F14*)=Sof(F15*)=1-FVAR(6)
 Sof(F14)=Sof(F15)=FVAR(6)
 Fixed Sof: O1(0.5) C109(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C110(0.5)
 H11A(0.5) H11B(0.5) C111(0.5) H11C(0.5) H11D(0.5) C112(0.5) H11E(0.5)
 H11F(0.5) H11G(0.5) O2(0.5) C113(0.5) H11H(0.5) H11I(0.5) H11J(0.5) C114(0.5)
 H11K(0.5) H11L(0.5) C115(0.5) H11M(0.5) H11N(0.5) C116(0.5) H11O(0.5)
 H11P(0.5) H11Q(0.5) O3(0.5) C117(0.5) H11R(0.5) H11S(0.5) H11T(0.5) C118(0.5)
 H11U(0.5) H11V(0.5) C119(0.5) H11W(0.5) H11X(0.5) C120(0.5) H12A(0.5)
 H12B(0.5) H12C(0.5)
5.a Free rotating group:
 O1(C109,C110,C111,C112), O2(C113,C114,C115,C116), O3(C117,C118,C119,C120)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C110(H11A,H11B), C111(H11C,H11D), C114(H11K,H11L),
 C115(H11M,H11N), C118(H11U,H11V), C119(H11W,H11X)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C20(H20), C26(H26), 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), C54(H54), C55(H55), C56(H56), C57(H57),
 C58(H58), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C66(H66), C67(H67),
  C68(H68), C69(H69), C70(H70), C72(H72), C73(H73), C74(H74), C75(H75),
 C76(H76), C78(H78), C80(H80), C82(H82), C86(H86), C88(H88), C90(H90), C94(H94),
  C96(H96), C98(H98), C102(H102), C104(H104), C106(H106)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,
 H13B,H13C), C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C29(H29A,H29B,H29C), C109(H10A,H10B,H10C), C112(H11E,H11F,
 H11G), C113(H11H,H11I,H11J), C116(H11O,H11P,H11Q), C117(H11R,H11S,H11T),
 C120(H12A,H12B,H12C)
;
_shelx_res_checksum              92894
_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 1.935
_oxdiff_exptl_absorpt_empirical_full_min 0.695