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_1575204
_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         'C71 H94 K N3 O3 U, 2(C6 H14)'
_chemical_formula_sum            'C83 H122 K N3 O3 U'
_chemical_formula_weight         1486.96
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-22
_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                90
_cell_angle_beta                 93.4484(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.81503(15)
_cell_length_b                   15.69327(17)
_cell_length_c                   33.7005(3)
_cell_measurement_reflns_used    19382
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4490
_cell_measurement_theta_min      3.0530
_cell_volume                     7821.05(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.137a 64-bit (release 10-09-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (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 0.996
_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    -72.00 -28.00   1.00    9.00    --  -40.66 121.00 -41.00   44
  2  \w   -111.00 -86.00   1.00    9.00    --  -40.66-152.00  75.00   25
  3  \w     53.00  78.00   1.00    9.00    --   40.66-152.00  75.00   25
  4  \w     34.00  59.00   1.00    9.00    --   40.66-121.00-124.00   25
  5  \w     47.00  72.00   1.00   35.00    --  104.84-121.00-124.00   25
  6  \w     92.00 131.00   1.00   35.00    --  104.84-152.00  75.00   39
  7  \w     98.00 123.00   1.00   35.00    --  104.84 152.00 118.00   25
  8  \w    122.00 177.00   1.00   35.00    --  104.84 121.00 -41.00   55
  9  \w     -8.00  23.00   1.00    9.00    --  -40.66  38.00-150.00   31
 10  \w   -115.00 -16.00   1.00    9.00    --  -40.66 -38.00  30.00   99
 11  \w    -65.00 -39.00   1.00    9.00    --  -40.66  38.00-150.00   26
 12  \w     28.00  94.00   1.00    9.00    --   40.66-125.00-150.00   66
 13  \w    104.00 176.00   1.00   35.00    --  104.84  77.00 150.00   72
 14  \w    104.00 177.00   1.00   35.00    --  104.84  77.00 -60.00   73
 15  \w     42.00 107.00   1.00   35.00    --  104.84-111.00 -90.00   65
 16  \w    130.00 156.00   1.00   35.00    --  104.84 111.00  60.00   26
 17  \w    125.00 178.00   1.00   35.00    --  104.84 111.00  90.00   53
 18  \w    104.00 130.00   1.00   35.00    --  104.84 111.00-120.00   26
 19  \w     58.00 139.00   1.00   35.00    --  104.84-178.00-150.00   81
 20  \w    108.00 174.00   1.00   35.00    --  104.84  77.00-150.00   66
;
_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      -0.0372303000
_diffrn_orient_matrix_UB_12      -0.0118380000
_diffrn_orient_matrix_UB_13      0.0413626000
_diffrn_orient_matrix_UB_21      0.0060528000
_diffrn_orient_matrix_UB_22      0.0968927000
_diffrn_orient_matrix_UB_23      0.0070667000
_diffrn_orient_matrix_UB_31      -0.0970582000
_diffrn_orient_matrix_UB_32      0.0105301000
_diffrn_orient_matrix_UB_33      -0.0183788000
_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  0.0531
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            41957
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.676
_diffrn_reflns_theta_min         3.107
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.668
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.455
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.137a (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 brown'
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       prism
_exptl_crystal_F_000             3104
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.076
_refine_diff_density_max         1.928
_refine_diff_density_min         -2.402
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     924
_refine_ls_number_reflns         15116
_refine_ls_number_restraints     215
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0627P)^2^+1.3814P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12580
_reflns_number_total             15116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp194
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_database_code               1575204
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C83 H122 N3 O3 K1 U1'
_shelx_estimated_absorpt_t_max   0.631
_shelx_estimated_absorpt_t_min   0.294
_olex2_refinement_description
;
1. Restrained distances
 C81-C83 = C82-C84 = C83-C85 = C84-C86 = C91-C93 = C92-C94 = C93-C95 = C94-C96
 2.5 with sigma of 0.04
 C82-C81 \\sim C83-C82 \\sim C84-C83 \\sim C85-C84 \\sim C86-C85 \\sim C91-C92
\\sim C92-C93 \\sim C93-C94
 \\sim C94-C95 \\sim C95-C96
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C91) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C94) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C96) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C80) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C81, C82, C83, C84, C85, C86, C91, C92, C93, C94, C95, C96
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C93)=
 Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(C95)=Sof(H95A)=Sof(H95B)=
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=1-FVAR(2)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=
 Sof(H83A)=Sof(H83B)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C85)=Sof(H85A)=Sof(H85B)=
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=FVAR(2)
 Fixed X: U1(0.666821)
 Fixed Y: U1(0.712529)
 Fixed Z: U1(0.664721)
5.a Ternary CH refined with riding coordinates:
 C33(H33), C36(H36), C45(H45), C48(H48)
5.b Secondary CH2 refined with riding coordinates:
 C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,
 H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B),
 C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C76(H76A,H76B), C77(H77A,H77B),
  C78(H78A,H78B), C79(H79A,H79B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,
 H84B), C85(H85A,H85B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B),
 C95(H95A,H95B)
5.c Me refined with riding coordinates:
 C96(H96A,H96B,H96C)
5.d 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), C52(H52), C53(H53), C54(H54), C55(H55), C59(H59), C60(H60),
  C61(H61), C62(H62)
5.e 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), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), 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), C75(H75A,H75B,H75C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C86(H86A,H86B,H86C), C91(H91A,H91B,H91C)
;
_shelx_res_checksum              12048
_olex2_date_sample_data_collection 2024-09-17
_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 2.650
_oxdiff_exptl_absorpt_empirical_full_min 0.290