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_1576580
_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         'C67 H77 Fe2 N6 O P, 1.5(C4 H10 O)'
_chemical_formula_sum            'C73 H92 Fe2 N6 O2.5 P'
_chemical_formula_weight         1236.19
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2024-08-02 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.414(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3808(4)
_cell_length_b                   21.0758(7)
_cell_length_c                   30.3435(10)
_cell_measurement_reflns_used    19653
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.2450
_cell_measurement_theta_min      2.6790
_cell_volume                     6583.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'Dectris Pilatus3 R 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -12.00  90.00   0.50   40.00    --    8.12  21.00-160.00  204
  2  \w    -73.00   6.00   0.50   40.00    --    8.12 -21.00  32.00  158
  3  \w    -18.00  25.00   0.50   40.00    --    8.12  77.00  30.00   86
  4  \w    -11.00  59.00   0.50   40.00    --    8.12  57.00  60.00  140
  5  \w    -18.00  25.00   0.50   40.00    --    8.12  77.00 150.00   86
  6  \w    -34.00  25.00   0.50   40.00    --   -8.43  77.00-150.00  118
  7  \w    -25.00  18.00   0.50   40.00    --   -8.43 -77.00-150.00   86
  8  \w    -34.00  23.00   0.50   40.00    --   -8.43  77.00 120.00  114
;
_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      0.0134416000
_diffrn_orient_matrix_UB_12      0.0040507000
_diffrn_orient_matrix_UB_13      0.0233515000
_diffrn_orient_matrix_UB_21      0.0657756000
_diffrn_orient_matrix_UB_22      -0.0084481000
_diffrn_orient_matrix_UB_23      -0.0008238000
_diffrn_orient_matrix_UB_31      0.0155026000
_diffrn_orient_matrix_UB_32      0.0323250000
_diffrn_orient_matrix_UB_33      -0.0031481000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            102608
_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         28.282
_diffrn_reflns_theta_min         2.360
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.516
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64847
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       plank
_exptl_crystal_F_000             2636
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.012
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     980
_refine_ls_number_reflns         16303
_refine_ls_number_restraints     532
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0492P)^2^+9.8136P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1279
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12772
_reflns_number_total             16303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc10054b2.cif
_cod_data_source_block           3924_1OEtMe_1MeOEt
_cod_depositor_comments
'Adding full bibliography for 1576580--1576582.cif.'
_cod_original_formula_sum        'C73 H92 Fe2 N6 O2.50 P'
_cod_database_code               1576580
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.861
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, 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
 C60*-C59* = C69-C68 = C29*-C28* = C30*-C28* = C31*-C28* = C31-C28 = C29-C28 =
 C30-C28 = C72*-C73* = C72-C73
 1.54 with sigma of 0.01
 O1-C65 = O1-C68 = O1*-C56 = O1*-C59* = O2*-C72* = O2-C72 = O2-C71 = O2*-C71*
 1.45 with sigma of 0.01
 C67*-C66* = C66*-C65* = C65*-C64* = C64*-C63* = C63-C62 = C64-C63 = C65-C64 =
 C66-C65 = C67-C66 = C67-C62
 1.4 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C28 \\sim C28* \\sim C29 \\sim C29* \\sim C30 \\sim C30* \\sim C31 \\sim C31*:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C22 \\sim C23 \\sim C23* \\sim C24 \\sim C24* \\sim C25 \\sim C25*: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C76 \\sim O3 \\sim C75 \\sim C74 \\sim C77: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
O2* \\sim O2 \\sim C71 \\sim C72 \\sim C70 \\sim C73 \\sim C71* \\sim C72*
\\sim C73*: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
O1 \\sim C62 \\sim C63 \\sim C63* \\sim C64 \\sim C64* \\sim C65 \\sim C65*
\\sim C66 \\sim C66* \\sim C67 \\sim C67* \\sim C68 \\sim C68* \\sim C69:
within 2A with sigma of 0.003 and sigma for terminal atoms of 0.006 within 2A
O1* \\sim C59 \\sim C59* \\sim C60' \\sim C60*: within 2A with sigma of 0.003
and sigma for terminal atoms of 0.006 within 2A
4. Others
 Fixed Sof: O1(0.5) O1*(0.5) C23(0.75) H23A(0.75) H23B(0.75) H23C(0.75) C23*
 (0.25) H23D(0.25) H23E(0.25) H23F(0.25) C24(0.75) H24A(0.75) H24B(0.75)
 H24C(0.75) C24*(0.25) H24D(0.25) H24E(0.25) H24F(0.25) C25(0.75) H25A(0.75)
 H25B(0.75) H25C(0.75) C25*(0.25) H25D(0.25) H25E(0.25) H25F(0.25) C28(0.5) C28*
 (0.5) C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C29*(0.5) H29D(0.5) H29E(0.5)
 H29F(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C30*(0.5) H30D(0.5) H30E(0.5)
 H30F(0.5) C31(0.5) H31A(0.5) H31B(0.5) H31C(0.5) C31*(0.5) H31D(0.5) H31E(0.5)
 H31F(0.5) C59(0.5) H59A(0.5) H59B(0.5) H59C(0.5) C59*(0.5) H59D(0.25)
 H59E(0.25) H59F(0.25) H59G(0.25) C60'(0.25) H60A(0.25) H60B(0.25) H60C(0.25)
 C60*(0.25) H60D(0.25) H60E(0.25) H60F(0.25) C63(0.5) H63(0.5) C63*(0.5) H63*
 (0.5) C64(0.5) H64(0.5) C64*(0.5) H64*(0.5) C65(0.5) C65*(0.5) C66(0.5)
 H66(0.5) C66*(0.5) H66*(0.5) C67(0.5) H67(0.5) C67*(0.5) H67*(0.5) C68(0.5)
 H68A(0.5) H68B(0.5) C68*(0.5) H68C(0.5) H68D(0.5) H68E(0.5) C69(0.5) H69A(0.5)
 H69B(0.5) H69C(0.5) O2(0.55) O2*(0.45) H70A(0.55) H70B(0.55) H70C(0.55)
 H70D(0.45) H70E(0.45) H70F(0.45) C71(0.55) H71A(0.55) H71B(0.55) C71*(0.45)
 H71C(0.45) H71D(0.45) C72(0.55) H72A(0.55) H72B(0.55) C72*(0.45) H72C(0.45)
 H72D(0.45) C73(0.55) H73A(0.55) H73B(0.55) H73C(0.55) C73*(0.45) H73D(0.45)
 H73E(0.45) H73F(0.45) O3(0.5) C74(0.5) H74A(0.5) H74B(0.5) H74C(0.5) C75(0.5)
 H75A(0.5) H75B(0.5) C76(0.5) H76A(0.5) H76B(0.5) C77(0.5) H77A(0.5) H77B(0.5)
 H77C(0.5)
 Fixed X: H59D(0.884109) H59E(0.95815) H59F(1.024449) H59G(0.876559)
 Fixed Y: H59D(0.827261) H59E(0.869361) H59F(0.842669) H59G(0.828921)
 Fixed Z: H59D(0.42144) H59E(0.46149) H59F(0.4179) H59G(0.426559)
5.a Free rotating group:
 O3(C74,C75,C76,C77)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C68(H68A,H68B), C71(H71A,H71B), C71*(H71C,H71D), C72(H72A,
 H72B), C72*(H72C,H72D), C75(H75A,H75B), C76(H76A,H76B)
5.c Me refined with riding coordinates:
 C29(H29A,H29B,H29C), C29*(H29D,H29E,H29F), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C31*(H31D,H31E,H31F), C59(H59A,H59B,H59C), C68*(H68C,H68D,H68E),
 C70(H70A,H70B,H70C), C70(H70D,H70E,H70F), C74(H74A,H74B,H74C), C77(H77A,H77B,
 H77C)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C13(H13), C15(H15), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47),
  C48(H48), C49(H49), C50(H50), C54(H54), C55(H55), C57(H57), C58(H58),
 C63(H63), C63*(H63*), C64(H64), C64*(H64*), C66(H66), C66*(H66*), C67(H67),
 C67*(H67*)
5.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C23*(H23D,H23E,H23F), C24(H24A,H24B,
 H24C), C24*(H24D,H24E,H24F), C25(H25A,H25B,H25C), C25*(H25D,H25E,H25F),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C30*(H30D,H30E,H30F), C32(H32A,H32B,
 H32C), C60'(H60A,H60B,H60C), C60*(H60D,H60E,H60F), C69(H69A,H69B,H69C),
 C73(H73A,H73B,H73C), C73*(H73D,H73E,H73F)
;
_shelx_res_checksum              62577
_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 1.305
_oxdiff_exptl_absorpt_empirical_full_min 0.717