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_1575000
_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         'C42 H70 N4 O2 U, 2[C4H8O]'
_chemical_formula_sum            'C50 H86 N4 O4 U'
_chemical_formula_weight         1045.25
_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     heavy
_audit_creation_date             2024-11-06
_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                 96.971(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.1897(4)
_cell_length_b                   15.6587(6)
_cell_length_c                   19.7929(8)
_cell_measurement_reflns_used    6090
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.6540
_cell_measurement_theta_min      3.3210
_cell_volume                     4980.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_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    'SHELXS  (Sheldrick, 2008)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.965
_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    -85.00 -13.00   1.00   12.50    --  -40.66 124.00 -29.00   72
  2  \w   -112.00 -87.00   1.00   12.50    --  -40.66-147.00  86.00   25
  3  \w     50.00  75.00   1.00   12.50    --   40.66-147.00  86.00   25
  4  \w     42.00  79.00   1.00   12.50    --   40.66-124.00-107.00   37
  5  \w     65.00 108.00   1.00   50.00    --  106.09-124.00-107.00   43
  6  \w    103.00 128.00   1.00   50.00    --  106.09 147.00 136.00   25
  7  \w    113.00 138.00   1.00   50.00    --  106.09 124.00 -29.00   25
  8  \w    102.00 128.00   1.00   50.00    --  106.09-147.00  86.00   26
  9  \w   -112.00 -14.00   1.00   12.50    --  -40.66 -57.00  60.00   98
 10  \w    -31.00  -4.00   1.00   12.50    --   40.66 -38.00-180.00   27
 11  \w     18.00 114.00   1.00   12.50    --   40.66  38.00-180.00   96
 12  \w     19.00  46.00   1.00   12.50    --   40.66 -38.00-150.00   27
 13  \w     79.00 107.00   1.00   50.00    --  106.09 -94.00-120.00   28
 14  \w    104.00 178.00   1.00   50.00    --  106.09  77.00 -30.00   74
 15  \w     94.00 121.00   1.00   50.00    --  106.09 -77.00  60.00   27
 16  \w    143.00 170.00   1.00   50.00    --  106.09  77.00-120.00   27
 17  \w     97.00 176.00   1.00   50.00    --  106.09 125.00 150.00   79
 18  \w     24.00 105.00   1.00   50.00    --  106.09 -94.00 -90.00   81
 19  \w     37.00  88.00   1.00   50.00    --  106.09 -77.00  60.00   51
 20  \w    103.00 164.00   1.00   50.00    --  106.09  77.00-150.00   61
 21  \w    106.00 175.00   1.00   50.00    --  106.09  77.00  60.00   69
;
_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      0.0694789000
_diffrn_orient_matrix_UB_12      0.0352463000
_diffrn_orient_matrix_UB_13      0.0527618000
_diffrn_orient_matrix_UB_21      0.0211918000
_diffrn_orient_matrix_UB_22      -0.0915196000
_diffrn_orient_matrix_UB_23      0.0248813000
_diffrn_orient_matrix_UB_31      0.0625526000
_diffrn_orient_matrix_UB_32      -0.0081029000
_diffrn_orient_matrix_UB_33      -0.0523859000
_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  0.0975
_diffrn_reflns_av_unetI/netI     0.1270
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            27066
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.642
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.514
_exptl_absorpt_correction_T_max  0.639
_exptl_absorpt_correction_T_min  0.206
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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 intense gold'
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       prism
_exptl_crystal_F_000             2152
_exptl_crystal_size_max          0.366
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.069
_refine_diff_density_max         1.946
_refine_diff_density_min         -2.135
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         9714
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0633
_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^)+(0.0500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1589
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6059
_reflns_number_total             9714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03694a2.cif
_cod_data_source_block           lm5
_cod_depositor_comments
'Adding full bibliography for 1574998--1575000.cif.'
_cod_database_code               1575000
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C50 H86 N4 O4 U1'
_shelx_estimated_absorpt_t_max   0.560
_shelx_estimated_absorpt_t_min   0.128
_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
 C44-C46 \\sim C46-C45 \\sim C44-C45
 with sigma of 0.02
 C20-C19 \\sim C21-C19 \\sim C22-C19 \\sim C44-C43 \\sim C45-C43 \\sim C46-C43
 with sigma of 0.02
 C19-C15 \\sim C43-C15
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C43 \\sim C44 \\sim C45 \\sim C46:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(1)
 Sof(C19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B),
 C34(H34A,H34B)
5.b Me refined with riding coordinates:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C30(H30), C32(H32)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 296 electrons were 
found in a volume of 1320\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C4H8O] per Asymmetric Unit 
which account for 320 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              45965
_shelx_fab_checksum              77790
_olex2_date_sample_data_collection 2023-05-23
_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 2.536
_oxdiff_exptl_absorpt_empirical_full_min 0.457