Facile N-C bond cleavage and arene reduction by a transient uranium(ii) complex.
Shivaraam, R. A. Keerthi; Maria, Leonor; Rajeshkumar, Thayalan; Scopelliti, Rosario; Živković, Ivica; Sienkiewicz, Andrzej; Maron, Laurent; Mazzanti, Marinella; Chemical science 16 (2025) 14242–14251; doi:10.1039/d5sc03694a

data_1574998
_publ_section_title
;
 Facile N-C bond cleavage and arene reduction by a transient uranium(ii)
 complex.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              14242
_journal_page_last               14251
_journal_paper_doi               10.1039/d5sc03694a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C90 H146 N8 O4 U2, 3.6[C7H8]'
_chemical_formula_sum            'C115.2 H174.8 N8 O4 U2'
_chemical_formula_weight         2211.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-11-26
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-18 deposited with the CCDC.	2025-06-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.162(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.8734(7)
_cell_length_b                   20.7159(8)
_cell_length_c                   26.4929(3)
_cell_measurement_reflns_used    11851
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.4630
_cell_measurement_theta_min      2.6960
_cell_volume                     5387.5(4)
_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      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.962
_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     67.00 108.00   0.50    1.50    --   63.87  18.00 169.00   82
  2  \w    -76.00 -50.00   0.50    1.50    --  -64.59 -18.00   1.00   52
  3  \w   -114.00 -77.00   0.50    1.50    --  -71.12 -18.00   1.00   74
  4  \w     96.00 122.00   0.50    1.50    --   75.73  18.00 169.00   52
  5  \w     45.00  75.00   0.50    1.50    --   76.61  18.00 169.00   60
  6  \w     30.00  55.00   0.50    1.50    --   63.87 -95.00 150.00   50
  7  \w     28.00 101.00   0.50    1.50    --   63.87   0.00 -60.00  146
  8  \w    -57.00 -27.00   0.50    1.50    --  -64.59   0.00  60.00   60
  9  \w    -91.00 -43.00   0.50    1.50    --  -64.59 125.00-150.00   96
 10  \w    -85.00 -32.00   0.50    1.50    --  -71.12 111.00 150.00  106
 11  \w    -71.00 -40.00   0.50    1.50    --  -71.12   0.00-180.00   62
 12  \w    -86.00 -31.00   0.50    1.50    --  -71.12 111.00-180.00  110
 13  \w    -78.00 -39.00   0.50    1.50    --  -71.12 111.00  30.00   78
 14  \w    -70.00 -37.00   0.50    1.50    --  -71.12   0.00-150.00   66
 15  \w     53.00  79.00   0.50    1.50    --   75.73-111.00-120.00   52
 16  \w     38.00  63.00   0.50    1.50    --   75.73 -95.00-180.00   50
 17  \w     68.00  93.00   0.50    1.50    --   75.73-111.00 120.00   50
 18  \w     66.00  92.00   0.50    1.50    --   75.73-111.00 -60.00   52
 19  \w     59.00  93.00   0.50    1.50    --   76.61-125.00-120.00   68
 20  \w     48.00 103.00   0.50    1.50    --   76.61-125.00 -90.00  110
 21  \w     78.00 103.00   0.50    1.50    --   76.61-125.00 -30.00   50
 22  \w     71.00 102.00   0.50    1.50    --   76.61-125.00 120.00   62
 23  \w     48.00  74.00   0.50    1.50    --   76.61 -95.00   0.00   52
 24  \w     54.00  80.00   0.50    1.50    --   76.61 -95.00 150.00   52
 25  \w     55.00  81.00   0.50    1.50    --   76.61 -95.00 120.00   52
 26  \w     51.00  87.00   0.50    1.50    --   76.61-125.00  90.00   72
 27  \w     60.00 103.00   0.50    1.50    --   76.61-125.00   0.00   86
 28  \w     42.00  80.00   0.50    1.50    --   76.61 -95.00 -60.00   76
 29  \w     71.00 116.00   0.50    1.50    --   79.75   1.00-145.30   90
 30  \w     65.00 126.00   0.50    1.50    --   79.75  21.00  48.01  122
 31  \w     98.00 124.00   0.50    1.50    --   79.75  19.00 -13.93   52
 32  \w     54.00  83.00   0.50    1.50    --   79.75  19.00 -13.93   58
 33  \w     40.00 101.00   0.50    1.50    --   79.75-115.00 -73.44  122
 34  \w     70.00  96.00   0.50    1.50    --   79.75  21.00 -94.17   52
 35  \w     42.00  82.00   0.50    1.50    --   79.75   0.00-160.30   80
 36  \w     66.00 107.00   0.50    1.50    --   79.75  23.00   2.58   82
 37  \w     58.00  84.00   0.50    1.50    --   79.75  17.00-165.59   52
 38  \w     53.00 103.00   0.50    1.50    --   79.75   5.00 137.30  100
 39  \w     63.00 106.00   0.50    1.50    --   79.75   6.00 -60.43   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1522960000
_diffrn_orient_matrix_UB_12      0.0013999000
_diffrn_orient_matrix_UB_13      0.0198372000
_diffrn_orient_matrix_UB_21      -0.0365991000
_diffrn_orient_matrix_UB_22      0.0179351000
_diffrn_orient_matrix_UB_23      0.0533287000
_diffrn_orient_matrix_UB_31      -0.0061650000
_diffrn_orient_matrix_UB_32      -0.0720615000
_diffrn_orient_matrix_UB_33      0.0136232000
_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  0.0734
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            57981
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         2.714
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.801
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.281
_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 gold'
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_description       needle
_exptl_crystal_F_000             2276
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.456
_refine_diff_density_min         -1.936
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     512
_refine_ls_number_reflns         9157
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0692P)^2^+0.9433P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1092
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7365
_reflns_number_total             9157
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 3.2647\% 
around [0.33 -0.78 -0.54] (reciprocal) or [0.86 -0.48 -0.17] (direct)
Component 3 rotated by -141.4619\% 
around [0.32 0.11 0.94] (reciprocal) or [0.93 0.06 0.37] (direct)
Component 4 rotated by -179.8860\% 
around [-0.01 1.00 -0.00] (reciprocal) or [-0.03 1.00 -0.00] (direct)
;
_cod_data_source_file            d5sc03694a2.cif
_cod_data_source_block           ks1070c
_cod_depositor_comments
'Adding full bibliography for 1574998--1575000.cif.'
_cod_original_formula_sum        'C115.20 H174.80 N8 O4 U2'
_cod_database_code               1574998
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C111 H170 N8 O4 U2'
_shelx_estimated_absorpt_t_max   0.709
_shelx_estimated_absorpt_t_min   0.277
_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
 C39-C38 \\sim C46-C38 \\sim C40-C38 \\sim C47-C38 \\sim C41-C38 \\sim C48-C38
 with sigma of 0.02
 C46-C48 \\sim C48-C47 \\sim C46-C47
 with sigma of 0.02
 C39-C41 \\sim C41-C40 \\sim C39-C40
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C39 \\sim C46 \\sim C38 \\sim C40 \\sim C47 \\sim C48 \\sim C41: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=1-FVAR(1)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B),
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B)
5.b Me refined with riding coordinates:
 C47(H47A,H47B,H47C), C46(H46A,H46B,H46C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C8(H8), C33(H33), C35(H35)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C27(H27A,
 H27B,H27C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C48(H48A,H48B,
 H48C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 350 electrons were 
found in a volume of 1556\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
4[C7H8] per formula unit 
which account for 400 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              2646
_shelx_fab_checksum              95324
_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 1.940
_oxdiff_exptl_absorpt_empirical_full_min 0.473
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               4