Room temperature dinitrogen cleavage and hydrogenation with organometallic complexes of uranium.
Shephard, Angus C. G.; Pedussaut, Lucie; De Marchi, Linda; Demonti, Luca; Rajeshkumar, Thayalan; Casaretto, Nicolas; Maron, Laurent; Danoun, Grégory; Simler, Thomas; Nocton, Grégory; Chemical science 16 (2025) 21334–21345; doi:10.1039/d5sc07194a

data_1575978
_publ_section_title
;
 Room temperature dinitrogen cleavage and hydrogenation with
 organometallic complexes of uranium.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              21334
_journal_page_last               21345
_journal_paper_doi               10.1039/d5sc07194a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C55 H97 N2 O U2'
_chemical_formula_sum            'C55 H97 N2 O U2'
_chemical_formula_weight         1278.40
_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             2025-05-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-13 deposited with the CCDC.	2025-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.426(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5775(12)
_cell_length_b                   25.372(4)
_cell_length_c                   21.043(3)
_cell_measurement_reflns_used    15506
_cell_measurement_temperature    150
_cell_measurement_theta_max      24.92
_cell_measurement_theta_min      1.67
_cell_volume                     5535.4(13)
_computing_cell_refinement
;
X-Area Recipe 2.0.2 (STOE, 2024)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.194.0 (STOE, 2023)
;
_computing_data_reduction
;
X-Area Integrate 2.5.18.0 (STOE, 2024)
X-Area LANA 2.8.4 (STOE, 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_temperature      150.15
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
 684 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            41618
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         2.122
_exptl_absorpt_coefficient_mu    5.880
_exptl_absorpt_correction_T_max  0.4213
_exptl_absorpt_correction_T_min  0.2439
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2532
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         4.261
_refine_diff_density_min         -2.047
_refine_diff_density_rms         0.184
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     767
_refine_ls_number_reflns         10873
_refine_ls_number_restraints     930
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0761P)^2^+42.8388P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1376
_refine_ls_wR_factor_ref         0.1487
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9031
_reflns_number_total             10873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07194a3.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1575976--1575980.cif.'
_cod_original_cell_volume        5535.4(12)
_cod_database_code               1575978
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.493
_shelx_estimated_absorpt_t_min   0.372
_diffrn_oxdiff_ac3_digest_hkl    414318da4f98b6e38d204b9e79681fc9a94476
_olex2_refinement_description
;
1. Restrained distances
 C28-C23 \\sim C29-C23 \\sim C24-C23 \\sim C25-C23 \\sim C26-C23 \\sim C27-C23
 with sigma of 0.02
 C44-C43 \\sim C69-C68 \\sim C45-C43 \\sim C70-C68 \\sim C71-C68 \\sim C46-C43
\\sim C63-C60 \\sim C53-C51
 \\sim C61-C60 \\sim C52-C51 \\sim C54-C60 \\sim C62-C51 \\sim C50-C47 \\sim
C67-C64 \\sim C48-C47 \\sim C65-
 C64 \\sim C49-C47 \\sim C66-C64
 with sigma of 0.02
 C68-C58 \\sim C43-C38 \\sim C60-C55 \\sim C51-C40 \\sim C64-C56 \\sim C47-C41
 with sigma of 0.02
 O1-C73 \\sim O1-C72 \\sim O1-C77 \\sim O1-C75
 with sigma of 0.02
 C74-C73 \\sim C74-C72 \\sim C76-C77 \\sim C75-C76
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C38 \\sim C42 \\sim C41 \\sim C40 \\sim C39 \\sim C43 \\sim C44 \\sim C45 \\sim
C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim
C54 \\sim C55 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 2A
C23 \\sim C24 \\sim C26 \\sim C28 \\sim C25 \\sim C27 \\sim C29: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O1 \\sim C74 \\sim C76 \\sim C72 \\sim C75 \\sim C73 \\sim C77: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 C38, C42, C41, C40, C39, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52,
 C53, C54, C55, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70, C71
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=1-FVAR(1)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(H76D)=Sof(H76E)=Sof(H76F)=Sof(C73)=
 Sof(H73A)=Sof(H73B)=Sof(C77)=Sof(H77A)=Sof(H77B)=1-FVAR(2)
 Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C72)=
 Sof(H72A)=Sof(H72B)=Sof(C75)=Sof(H75A)=Sof(H75B)=FVAR(2)
 Sof(C58)=Sof(C57)=Sof(H57)=Sof(C56)=Sof(C55)=Sof(C59)=Sof(H59)=Sof(C60)=
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64)=Sof(C65)=Sof(H65A)=Sof(H65B)=
 Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67)=Sof(H67A)=Sof(H67B)=
 Sof(H67C)=Sof(C68)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=1-FVAR(3)
 Sof(C38)=Sof(C42)=Sof(H42)=Sof(C41)=Sof(C40)=Sof(C39)=Sof(H39)=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)=Sof(C47)=Sof(C48)=Sof(H48A)=Sof(H48B)=
 Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=
 Sof(H50C)=Sof(C51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
5.a :
 C38(C42,C41,C40,C39), C58(C57,C56,C55,C59)
5.b Secondary CH2 refined with riding coordinates:
 C72(H72A,H72B), C75(H75A,H75B), C73(H73A,H73B), C77(H77A,H77B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C19(H19), C22(H22), C42(H42), C39(H39), C57(H57), C59(H59)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C74(H74A,H74B,H74C), C74(H74D,H74E,H74F), C76(H76A,H76B,H76C), C76(H76D,H76E,
 H76F), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C44(H44A,
 H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C),
 C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C29(H29A,
 H29B,H29C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C),
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C)
;
_shelx_res_checksum              91973
_olex2_submission_special_instructions 'No special instructions were received'