C-C bond cleavage and carbonylation enabled by an NNN-pincer uranium scaffold <i>via</i> metal-arene interaction.
Pang, Yue; Rajeshkumar, Thayalan; Scopelliti, Rosario; Maron, Laurent; Mazzanti, Marinella; Chemical science 16 (2025) 16101–16109; doi:10.1039/d5sc04248h

data_1575207
_publ_section_title
;
 C-C bond cleavage and carbonylation enabled by an NNN-pincer uranium
 scaffold <i>via</i> metal-arene interaction.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              16101
_journal_page_last               16109
_journal_paper_doi               10.1039/d5sc04248h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C84 H118 K N3 O7 U, 2(C4 H8 O)'
_chemical_formula_sum            'C92 H134 K N3 O9 U'
_chemical_formula_weight         1703.14
_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             2024-11-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-21 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                89.5052(15)
_cell_angle_beta                 75.2450(17)
_cell_angle_gamma                69.4982(18)
_cell_formula_units_Z            2
_cell_length_a                   13.3940(3)
_cell_length_b                   14.0175(2)
_cell_length_c                   25.0941(5)
_cell_measurement_reflns_used    27456
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      76.1980
_cell_measurement_theta_min      3.8580
_cell_volume                     4250.57(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.954
_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    -66.00  31.00   1.00    2.00    --  -40.79  35.00 -48.00   97
  2  \w   -116.00 -40.00   1.00    2.00    --  -40.79 -35.00 154.00   76
  3  \w     -8.00  17.00   1.00    2.00    --   40.79 -35.00 154.00   25
  4  \w     45.00 114.00   1.00    2.00    --   40.79  35.00 -48.00   69
  5  \w     38.00 137.00   1.00    8.00    --  112.00 -35.00 154.00   99
  6  \w    113.00 175.00   1.00    8.00    --  112.00  35.00 -48.00   62
  7  \w    -74.00 -45.00   1.00    2.00    --  -40.79 125.00 -30.00   29
  8  \w    -40.00 -11.00   1.00    2.00    --  -40.79 125.00  60.00   29
  9  \w     56.00  81.00   1.00    2.00    --   40.79 -99.00  60.00   25
 10  \w    -28.00  67.00   1.00    2.00    --   40.79 -57.00   0.00   95
 11  \w     35.00  92.00   1.00    2.00    --   40.79-125.00-180.00   57
 12  \w     35.00  89.00   1.00    2.00    --   40.79-125.00   0.00   54
 13  \w     42.00  67.00   1.00    8.00    --  112.00 -61.00  60.00   25
 14  \w     40.00  93.00   1.00    8.00    --  112.00-111.00 -30.00   53
 15  \w    129.00 177.00   1.00    8.00    --  112.00  77.00-120.00   48
 16  \w     60.00 107.00   1.00    8.00    --  112.00-111.00-120.00   47
 17  \w    108.00 166.00   1.00    8.00    --  112.00  77.00 120.00   58
 18  \w    105.00 140.00   1.00    8.00    --  112.00 111.00-150.00   35
 19  \w     39.00 109.00   1.00    8.00    --  112.00-111.00  60.00   70
 20  \w     45.00 108.00   1.00    8.00    --  112.00-111.00-180.00   63
 21  \w     91.00 174.00   1.00    8.00    --  112.00  61.00 -90.00   83
 22  \w    108.00 172.00   1.00    8.00    --  112.00  77.00-150.00   64
 23  \w     54.00 109.00   1.00    8.00    --  112.00-111.00 -60.00   55
 24  \w    104.00 131.00   1.00    8.00    --  112.00 111.00 -30.00   27
 25  \w     61.00  90.00   1.00    8.00    --  112.00-111.00 -90.00   29
 26  \w     67.00 104.00   1.00    8.00    --  112.00-111.00  30.00   37
 27  \w     42.00 109.00   1.00    8.00    --  112.00-111.00   0.00   67
 28  \w     50.00  89.00   1.00    8.00    --  112.00-111.00 150.00   39
 29  \w     75.00 101.00   1.00    8.00    --  112.00 -61.00  60.00   26
 30  \w     63.00  90.00   1.00    8.00    --  112.00 -45.00-120.00   27
 31  \w    110.00 176.00   1.00    8.00    --  112.00  77.00-180.00   66
 32  \w    153.00 178.00   1.00    8.00    --  112.00 111.00-150.00   25
 33  \w     86.00 112.00   1.00    8.00    --  112.00  45.00-150.00   26
 34  \w    134.00 161.00   1.00    8.00    --  112.00  45.00-150.00   27
 35  \w     61.00 109.00   1.00    8.00    --  112.00-111.00-150.00   48
 36  \w    104.00 129.00   1.00    8.00    --  112.00  77.00 -60.00   25
 37  \w    149.00 178.00   1.00    8.00    --  112.00  77.00 -60.00   29
 38  \w     40.00 109.00   1.00    8.00    --  112.00-111.00  90.00   69
 39  \w     82.00 109.00   1.00    8.00    --  112.00-111.00 120.00   27
 40  \w     55.00  81.00   1.00    8.00    --  112.00 -94.00-150.00   26
 41  \w     37.00  64.00   1.00    8.00    --  112.00 -94.00  30.00   27
 42  \w     61.00 113.00   1.00    8.00    --  112.00 178.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1158798000
_diffrn_orient_matrix_UB_12      0.0072157000
_diffrn_orient_matrix_UB_13      -0.0170958000
_diffrn_orient_matrix_UB_21      0.0504635000
_diffrn_orient_matrix_UB_22      -0.1132872000
_diffrn_orient_matrix_UB_23      -0.0228245000
_diffrn_orient_matrix_UB_31      -0.0166594000
_diffrn_orient_matrix_UB_32      0.0314820000
_diffrn_orient_matrix_UB_33      -0.0570022000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            20056
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.394
_diffrn_reflns_theta_min         3.623
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.259
_exptl_absorpt_correction_T_max  0.848
_exptl_absorpt_correction_T_min  0.316
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (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            'clear dark orange'
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_description       plate
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.259
_exptl_crystal_size_min          0.169
_refine_diff_density_max         4.581
_refine_diff_density_min         -5.242
_refine_diff_density_rms         0.225
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.204
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1152
_refine_ls_number_reflns         20056
_refine_ls_number_restraints     1827
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0789
_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^)+(0.0651P)^2^+94.7281P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2238
_refine_ls_wR_factor_ref         0.2249
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19552
_reflns_number_total             20056
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9045\% 
around [-0.00 0.00 1.00] (reciprocal) or [-0.48 0.15 0.86] (direct)
;
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp230
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_original_cell_volume        4250.57(15)
_cod_database_code               1575207
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C92 H134 N3 O9 K1 U1'
_shelx_estimated_absorpt_t_max   0.418
_shelx_estimated_absorpt_t_min   0.257
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9669(10)
 0.0331(10)
2. 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
3. Restrained distances
 C92-C91 = C92-C93 = C94-C93
 1.54 with sigma of 0.02
 O8-C94 = O8-C91
 1.43 with sigma of 0.02
 C93-C91
 2.5 with sigma of 0.02
 C94-C92
 2.5 with sigma of 0.02
 K1-C91
 3.9 with sigma of 0.02
 O11-C106 = O11-C109
 1.43 with sigma of 0.02
 C107-C106
 1.54 with sigma of 0.02
 C107-C108
 1.54 with sigma of 0.02
 C109-C108
 1.54 with sigma of 0.02
 C106-C108
 2.5 with sigma of 0.02
 C109-C107
 2.5 with sigma of 0.02
 C108-O11
 2.4 with sigma of 0.02
 C107-O11
 2.4 with sigma of 0.02
 C74-C73
 1.54 with sigma of 0.02
 K1-O7 \\sim K1-O8
 with sigma of 0.02
 C86-C85 \\sim C81-C82 \\sim C86-C83 \\sim C82-C83
 with sigma of 0.02
 O6-C85 \\sim O6-C81
 with sigma of 0.02
 C21-C20 \\sim C24-C20 \\sim C23-C20 \\sim C26-C20 \\sim C22-C20 \\sim C25-C20
 with sigma of 0.02
 C21-C22 \\sim C22-C23 \\sim C21-C23
 with sigma of 0.02
 C24-C25 \\sim C25-C26 \\sim C24-C26
 with sigma of 0.02
 C70-C72 \\sim C70-C69 \\sim C71-C69 \\sim C71-C72
 with sigma of 0.02
 C98-C97 \\sim C98-C103 \\sim C97-C96 \\sim C104-C103 \\sim C105-C104 \\sim
C96-C95
 with sigma of 0.02
 O9-C98 \\sim O9-C105 \\sim O9-C95
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O7 \\sim O8 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim
C93 \\sim C94: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
O6 \\sim C81 \\sim C82 \\sim C83 \\sim C85 \\sim C86: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C69 \\sim C70 \\sim C71 \\sim C72: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C20 \\sim C25 \\sim C22 \\sim C26 \\sim C23 \\sim C24 \\sim C21: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O9 \\sim C95 \\sim C98 \\sim C105 \\sim C96 \\sim C97 \\sim C103 \\sim C104:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O10 \\sim C102 \\sim C99 \\sim C100 \\sim C101 \\sim C106 \\sim C107 \\sim C108
\\sim C109 \\sim O11: within 2A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(O8)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C93)=
 Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=1-FVAR(1)
 Sof(O7)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(C89)=
 Sof(H89A)=Sof(H89B)=Sof(C90)=Sof(H90A)=Sof(H90B)=FVAR(1)
 Sof(H83C)=Sof(H83D)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C86)=Sof(H86A)=Sof(H86B)=
 1-FVAR(2)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H83A)=Sof(H83B)=
 FVAR(2)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=1-FVAR(3)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
 Sof(H69C)=Sof(H69D)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H72C)=Sof(H72D)=1-FVAR(4)
 Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H72A)=Sof(H72B)=FVAR(4)
 Sof(H98C)=Sof(H98D)=Sof(C103)=Sof(H10A)=Sof(H10B)=Sof(C104)=Sof(H10C)=
 Sof(H10D)=Sof(C105)=Sof(H10E)=Sof(H10F)=1-FVAR(5)
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(C97)=Sof(H97A)=
 Sof(H97B)=Sof(H98A)=Sof(H98B)=FVAR(5)
 Sof(O11)=Sof(C108)=Sof(H10M)=Sof(H10N)=Sof(C106)=Sof(H10O)=Sof(H10P)=
 Sof(C109)=Sof(H10Q)=Sof(H10R)=Sof(C107)=Sof(H10S)=Sof(H10T)=1-FVAR(6)
 Sof(O10)=Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(C100)=Sof(H10G)=Sof(H10H)=Sof(C101)=
 Sof(H10I)=Sof(H10J)=Sof(C102)=Sof(H10K)=Sof(H10L)=FVAR(6)
7.a Ternary CH refined with riding coordinates:
 C33(H33), C36(H36), C45(H45), C48(H48)
7.b Secondary CH2 refined with riding coordinates:
 C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,
 H68B), C69(H69A,H69B), C69(H69C,H69D), C70(H70A,H70B), C71(H71A,H71B),
 C72(H72A,H72B), C72(H72C,H72D), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
  C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,
 H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C83(H83C,H83D),
 C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B),
  C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,
 H93B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B),
 C98(H98A,H98B), C98(H98C,H98D), C99(H99A,H99B), C100(H10G,H10H), C101(H10I,
 H10J), C102(H10K,H10L), C103(H10A,H10B), C104(H10C,H10D), C105(H10E,H10F),
 C108(H10M,H10N), C106(H10O,H10P), C109(H10Q,H10R), C107(H10S,H10T)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C11(H11), C13(H13), C29(H29), C30(H30), C31(H31), C41(H41),
 C42(H42), C43(H43), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59), C60(H60),
  C61(H61), C62(H62)
7.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C)
;
_shelx_res_checksum              21967
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 3.413
_oxdiff_exptl_absorpt_empirical_full_min 0.331
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2