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_1574999
_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         'C54 H97 N4 O6 Si U, 0.5(C6 H14)'
_chemical_formula_sum            'C57 H104 N4 O6 Si U'
_chemical_formula_weight         1207.56
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-11-08
_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                84.700(3)
_cell_angle_beta                 80.165(2)
_cell_angle_gamma                82.473(2)
_cell_formula_units_Z            2
_cell_length_a                   11.2069(3)
_cell_length_b                   14.7053(5)
_cell_length_c                   18.7776(6)
_cell_measurement_reflns_used    11609
_cell_measurement_temperature    199.99(10)
_cell_measurement_theta_max      69.7940
_cell_measurement_theta_min      3.6700
_cell_volume                     3015.04(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.108a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.108a (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      199.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.975
_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    -62.00 -36.00   1.00    2.50    --  -43.01  72.00-175.00   26
  2  \w    119.00 162.00   1.00   10.00    --  103.18  72.00-175.00   43
  3  \w    106.00 133.00   1.00   10.00    --  103.18 -72.00  54.00   27
  4  \w     41.00  67.00   1.00   10.00    --  103.18 -72.00  54.00   26
  5  \w   -117.00 -19.00   1.00    2.50    --  -43.01 -37.00 150.00   98
  6  \w      6.00  31.00   1.00    2.50    --  -43.01  72.00-175.00   25
  7  \w    -84.00 -12.00   1.00    2.50    --  -43.01 125.00 -90.00   72
  8  \w    -30.00  -5.00   1.00    2.50    --   43.01 -37.00 -60.00   25
  9  \w     16.00 115.00   1.00    2.50    --   43.01  57.00 -90.00   99
 10  \w    -14.00  71.00   1.00    2.50    --   43.01 -72.00  54.00   85
 11  \w     39.00  66.00   1.00    2.50    --   43.01 -37.00 -60.00   27
 12  \w     77.00 109.00   1.00   10.00    --  103.18-111.00 -30.00   32
 13  \w     51.00 109.00   1.00   10.00    --  103.18-111.00-120.00   58
 14  \w     39.00 111.00   1.00   10.00    --  103.18 -61.00-150.00   72
 15  \w     31.00 128.00   1.00   10.00    --  103.18 -45.00 -90.00   97
 16  \w     68.00 106.00   1.00   10.00    --  103.18-111.00 150.00   38
 17  \w     32.00 126.00   1.00   10.00    --  103.18 -45.00  60.00   94
 18  \w    125.00 151.00   1.00   10.00    --  103.18 111.00  60.00   26
 19  \w     70.00  96.00   1.00   10.00    --  103.18-111.00  30.00   26
 20  \w     31.00 109.00   1.00   10.00    --  103.18-111.00  90.00   78
 21  \w    135.00 162.00   1.00   10.00    --  103.18  30.00  30.00   27
 22  \w    104.00 130.00   1.00   10.00    --  103.18  30.00  30.00   26
 23  \w     27.00 131.00   1.00   10.00    --  103.18 -30.00 150.00  104
 24  \w     51.00 178.00   1.00   10.00    --  103.18  15.00 150.00  127
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0149484000
_diffrn_orient_matrix_UB_12      0.0999960000
_diffrn_orient_matrix_UB_13      -0.0328127000
_diffrn_orient_matrix_UB_21      0.0636097000
_diffrn_orient_matrix_UB_22      0.0302969000
_diffrn_orient_matrix_UB_23      0.0588968000
_diffrn_orient_matrix_UB_31      0.1243677000
_diffrn_orient_matrix_UB_32      -0.0175312000
_diffrn_orient_matrix_UB_33      -0.0492292000
_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     0.0730
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13062
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.371
_diffrn_reflns_theta_min         3.039
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.138
_exptl_absorpt_correction_T_max  0.791
_exptl_absorpt_correction_T_min  0.355
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.108a (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 red'
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       plate
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.232
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.093
_refine_diff_density_max         3.762
_refine_diff_density_min         -1.696
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.975
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     708
_refine_ls_number_reflns         13062
_refine_ls_number_restraints     190
_refine_ls_restrained_S_all      0.970
_refine_ls_R_factor_all          0.0576
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0567P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0977
_refine_ls_wR_factor_ref         0.1023
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10759
_reflns_number_total             13062
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 5.8258\% 
around [-0.66 -0.49 -0.57] (reciprocal) or [-0.92 -0.33 -0.20] (direct)
Component 3 rotated by 14.8060\% 
around [0.24 0.06 0.97] (reciprocal) or [0.41 -0.05 0.91] (direct)
Component 4 rotated by -119.0580\% 
around [0.04 0.98 0.21] (reciprocal) or [-0.12 0.99 0.07] (direct)
;
_cod_data_source_file            d5sc03694a2.cif
_cod_data_source_block           ks820
_cod_depositor_comments
'Adding full bibliography for 1574998--1575000.cif.'
_cod_database_code               1574999
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C57 H104 N4 O6 Si1 U1'
_shelx_estimated_absorpt_t_max   0.518
_shelx_estimated_absorpt_t_min   0.254
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.522(3)
 0.2115(18) 0.1421(17) 0.1245(17)
2. 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
3. Restrained distances
 C58-C59 = C59-C60 = C60-C61 = C61-C62 = C62-C63
 1.52 with sigma of 0.02
 C58-C60 = C61-C63
 2.53 with sigma of 0.04
 C59-C61 = C60-C62
 2.54 with sigma of 0.04
 C58-C59 \\sim C59-C60 \\sim C60-C61 \\sim C61-C62 \\sim C62-C63
 with sigma of 0.02
 C58-C60 \\sim C60-C62 \\sim C59-C61 \\sim C61-C63
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C63) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C58) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C58, C59, C60, C61, C62, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(1)
 Fixed Sof: C58(0.5) H58A(0.5) H58B(0.5) H58C(0.5) C59(0.5) H59A(0.5)
 H59B(0.5) C60(0.5) H60A(0.5) H60B(0.5) C61(0.5) H61A(0.5) H61B(0.5) C62(0.5)
 H62A(0.5) H62B(0.5) C63(0.5) H63A(0.5) H63B(0.5) H63C(0.5)
7.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), C11(H11A,H11B),
 C27(H27A,H27B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B)
7.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C29(H29), C31(H31)
7.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              77680
_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 1.617
_oxdiff_exptl_absorpt_empirical_full_min 0.710
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               4