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_1575205
_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         'C126 H188 Cl4 K2 N6 O8 U2'
_chemical_formula_sum            'C126 H188 Cl4 K2 N6 O8 U2'
_chemical_formula_weight         2610.87
_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             2024-10-10
_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                103.3088(15)
_cell_angle_beta                 94.0723(15)
_cell_angle_gamma                107.2883(17)
_cell_formula_units_Z            1
_cell_length_a                   11.6846(2)
_cell_length_b                   15.7796(3)
_cell_length_c                   18.5920(3)
_cell_measurement_reflns_used    17071
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.5700
_cell_measurement_theta_min      4.1510
_cell_volume                     3149.13(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.111a 64-bit (release 27-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.112a (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      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_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   -114.00 -16.00   1.00    8.03    --  -41.04 -41.00 -75.00   98
  2  \w    -45.00   3.00   1.00    8.03    --  -41.04  41.00  77.00   48
  3  \w     -7.00  18.00   1.00    8.03    --   41.04 -41.00 -75.00   25
  4  \w     26.00 111.00   1.00    8.03    --   41.04  41.00  77.00   85
  5  \w     82.00 177.00   1.00   32.12    --  105.15  41.00  77.00   95
  6  \w     40.00 111.00   1.00   32.12    --  105.15 -41.00 -75.00   71
  7  \w    -84.00 -14.00   1.00    8.03    --  -41.04 125.00  90.00   70
  8  \w    -21.00  74.00   1.00    8.03    --   41.04 -77.00-180.00   95
  9  \w     31.00  92.00   1.00    8.03    --   41.04-125.00 -30.00   61
 10  \w     35.00 103.00   1.00   32.12    --  105.15 -94.00 -90.00   68
 11  \w    105.00 152.00   1.00   32.12    --  105.15  77.00   0.00   47
 12  \w     30.00 103.00   1.00   32.12    --  105.15 -94.00 -30.00   73
 13  \w     83.00 168.00   1.00   32.12    --  105.15  45.00 -30.00   85
 14  \w    120.00 145.00   1.00   32.12    --  105.15 111.00  60.00   25
 15  \w     37.00 109.00   1.00   32.12    --  105.15-111.00-150.00   72
 16  \w     64.00 109.00   1.00   32.12    --  105.15-111.00  60.00   45
 17  \w    105.00 149.00   1.00   32.12    --  105.15 111.00 -90.00   44
 18  \w    118.00 161.00   1.00   32.12    --  105.15 111.00  30.00   43
 19  \w    110.00 167.00   1.00   32.12    --  105.15 111.00   0.00   57
 20  \w    112.00 168.00   1.00   32.12    --  105.15 111.00-120.00   56
 21  \w     91.00 124.00   1.00   32.12    --  105.15 178.00-180.00   33
 22  \w     84.00 109.00   1.00   32.12    --  105.15-111.00  90.00   25
 23  \w     99.00 141.00   1.00   32.12    --  105.15 178.00-120.00   42
 24  \w     86.00 113.00   1.00   32.12    --  105.15 178.00 -60.00   27
;
_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      0.0556541000
_diffrn_orient_matrix_UB_12      -0.0686225000
_diffrn_orient_matrix_UB_13      -0.0449677000
_diffrn_orient_matrix_UB_21      0.1135573000
_diffrn_orient_matrix_UB_22      0.0803203000
_diffrn_orient_matrix_UB_23      -0.0004084000
_diffrn_orient_matrix_UB_31      0.0592768000
_diffrn_orient_matrix_UB_32      -0.0087685000
_diffrn_orient_matrix_UB_33      0.0734506000
_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  0.0365
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            26131
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.792
_diffrn_reflns_theta_min         3.041
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.976
_exptl_absorpt_correction_T_max  0.706
_exptl_absorpt_correction_T_min  0.278
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.112a (Rigaku Oxford Diffraction, 2024)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       prism
_exptl_crystal_F_000             1340
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.575
_refine_diff_density_min         -1.818
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     748
_refine_ls_number_reflns         12208
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0307
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0455P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0745
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11251
_reflns_number_total             12208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp060
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_original_cell_volume        3149.12(10)
_cod_database_code               1575205
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C63 H94 N3 O4 Cl2 K1 U1'
_chemical_oxdiff_usercomment     'dark green-yellow'
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.278
_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
2. Restrained distances
 O5-C65 \\sim O6-C68 \\sim O5-C62 \\sim O6-C62
 with sigma of 0.02
 O4-C61 \\sim O3-C61 \\sim O4-C58 \\sim O3-C56
 with sigma of 0.02
 C64-C65 \\sim C68-C67 \\sim C64-C63 \\sim C66-C67 \\sim C66-C62 \\sim C63-C62
 with sigma of 0.02
 C56-C57 \\sim C59-C58 \\sim C59-C60 \\sim C57-C60 \\sim C60-C61
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C65 \\sim C64 \\sim C67 \\sim C66 \\sim C63 \\sim C62 \\sim C68 \\sim O5 \\sim
O6 \\sim O4 \\sim O3 \\sim C58 \\sim C56 \\sim C59 \\sim C57 \\sim C60 \\sim
C61: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(O6)=Sof(H62C)=Sof(H62D)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=1-FVAR(1)
 Sof(O5)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=FVAR(1)
 Sof(O4)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H60C)=
 Sof(H60D)=Sof(H61C)=Sof(H61D)=1-FVAR(2)
 Sof(O3)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H60A)=
 Sof(H60B)=Sof(H61A)=Sof(H61B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45)
5.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,
 H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B),
 C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C60(H60C,H60D),
  C61(H61A,H61B), C61(H61C,H61D), C62(H62A,H62B), C62(H62C,H62D), C63(H63A,
 H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B),
 C68(H68A,H68B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C11(H11), C13(H13), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40)
5.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), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C)
;
_shelx_res_checksum              9865
_olex2_date_sample_data_collection 2024-02-28
_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 2.995
_oxdiff_exptl_absorpt_empirical_full_min 0.238