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_1575203
_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         'C63 H78 N3 O U, C20 H40 K O5'
_chemical_formula_sum            'C83 H118 K N3 O6 U'
_chemical_formula_weight         1530.93
_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
_atom_sites_solution_secondary   difmapp
_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
;
2024-10-22 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.5821(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.80343(14)
_cell_length_b                   22.6493(2)
_cell_length_c                   21.5753(2)
_cell_measurement_reflns_used    37854
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      36.2860
_cell_measurement_theta_min      1.5710
_cell_volume                     7671.69(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.135a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.137a 64-bit (release 10-09-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.135a (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 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.99(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 1.000
_diffrn_measured_fraction_theta_max 0.977
_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    -42.00 -10.00   0.50    4.00    --  -18.00 121.00 141.71   64
  2  \w    -29.00  12.00   0.50    4.00    --   18.00 -31.00 149.21   82
  3  \w    -29.00   2.00   0.50    4.00    --   14.00 -32.00 -89.73   62
  4  \w    -26.00  16.00   0.50    4.00    --   10.00 -25.00-148.15   84
  5  \w    -13.00  12.00   0.50    4.00    --   -0.78 102.00-174.07   50
  6  \w      9.00  37.00   0.50    4.00    --   -0.78  69.00-153.48   56
  7  \w    -11.00  14.00   0.50    4.00    --   -0.78  99.00 -43.70   50
  8  \w      0.00  26.00   0.50    4.00    --   -0.78  85.00  21.55   52
  9  \w    -10.00  16.00   0.50    4.00    --   -0.78 100.00  66.03   52
;
_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      0.0147421000
_diffrn_orient_matrix_UB_12      0.0205361000
_diffrn_orient_matrix_UB_13      0.0236125000
_diffrn_orient_matrix_UB_21      -0.0032799000
_diffrn_orient_matrix_UB_22      0.0230329000
_diffrn_orient_matrix_UB_23      -0.0224336000
_diffrn_orient_matrix_UB_31      -0.0425758000
_diffrn_orient_matrix_UB_32      0.0053398000
_diffrn_orient_matrix_UB_33      0.0058811000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            131598
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.318
_diffrn_reflns_theta_min         1.578
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.223
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.644
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.135a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'metallic dark brown'
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       prism
_exptl_crystal_F_000             3184
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.332
_refine_diff_density_min         -1.371
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     986
_refine_ls_number_reflns         36341
_refine_ls_number_restraints     401
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0344P)^2^+1.9459P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0747
_refine_ls_wR_factor_ref         0.0822
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25186
_reflns_number_total             36341
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp199
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1575203--1575209.cif.
;
_cod_original_cell_volume        7671.68(14)
_cod_database_code               1575203
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C83 H118 K N3 O6 U'
_chemical_oxdiff_usercomment     'crystallised from THF, Hexane'
_shelx_estimated_absorpt_t_max   0.808
_shelx_estimated_absorpt_t_min   0.618
_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
 C35A-C32 = C35B-C32 = C34A-C32 = C34B-C32 = C33A-C32 = C33B-C32
 1.54 with sigma of 0.02
 O5B-C79B = O5B-C76B
 1.44 with sigma of 0.02
 C78A-C77A
 1.52 with sigma of 0.02
 C79B-C78B = C77B-C76B
 1.53 with sigma of 0.02
 C78B-C77B
 1.54 with sigma of 0.02
 C82B-C81B
 1.5 with sigma of 0.02
 O6A-C80A = O6A-C83A
 1.45 with sigma of 0.02
 C81B-C80B = C82B-C83B
 1.5 with sigma of 0.02
 O6B-C80B = O6B-C83B
 1.45 with sigma of 0.02
 O5B-C78B = O5B-C77B = C79B-C77B = C78B-C76B
 2.38 with sigma of 0.04
 C35A-C34A \\sim C34A-C33A \\sim C33A-C35A
 with sigma of 0.02
 C33B-C34B \\sim C34B-C35B \\sim C35B-C33B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O2 \\sim O3 \\sim O4 \\sim O5A \\sim O6A \\sim C64 \\sim C65 \\sim C66 \\sim
C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim
C75 \\sim C76A \\sim C77A \\sim C78A \\sim C79A \\sim C80A \\sim C81A \\sim
C82A \\sim C83A: within 2A with sigma of 0.001 and sigma for terminal atoms of
2 within 2A
C32 \\sim C33A \\sim C33B \\sim C34A \\sim C34B \\sim C35A \\sim C35B: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
O6A \\sim O6B \\sim C80A \\sim C80B \\sim C81A \\sim C81B \\sim C82A \\sim C82B
\\sim C83A \\sim C83B: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
O5B \\sim C76B \\sim C77B \\sim C78B \\sim C79B: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
4. Others
 Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34B)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=Sof(C35B)=Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(1)
 Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(H34B)=
 Sof(H34C)=Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
 Sof(O6B)=Sof(C80B)=Sof(H80C)=Sof(H80D)=Sof(C81B)=Sof(H81C)=Sof(H81D)=
 Sof(C82B)=Sof(H82C)=Sof(H82D)=Sof(C83B)=Sof(H83C)=Sof(H83D)=1-FVAR(2)
 Sof(O6A)=Sof(C80A)=Sof(H80A)=Sof(H80B)=Sof(C81A)=Sof(H81A)=Sof(H81B)=
 Sof(C82A)=Sof(H82A)=Sof(H82B)=Sof(C83A)=Sof(H83A)=Sof(H83B)=FVAR(2)
 Sof(O5B)=Sof(C76B)=Sof(H76C)=Sof(H76D)=Sof(C77B)=Sof(H77C)=Sof(H77D)=
 Sof(C78B)=Sof(H78C)=Sof(H78D)=Sof(C79B)=Sof(H79C)=Sof(H79D)=1-FVAR(3)
 Sof(O5A)=Sof(C76A)=Sof(H76A)=Sof(H76B)=Sof(C77A)=Sof(H77A)=Sof(H77B)=
 Sof(C78A)=Sof(H78A)=Sof(H78B)=Sof(C79A)=Sof(H79A)=Sof(H79B)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C42(H42), C45(H45), C49(H49), C50(H50), C51(H51), C52(H52)
5.b Secondary CH2 refined with riding coordinates:
 C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), 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), C75(H75A,H75B), C76A(H76A,H76B), C76B(H76C,H76D), C77A(H77A,
 H77B), C77B(H77C,H77D), C78A(H78A,H78B), C78B(H78C,H78D), C79A(H79A,H79B),
 C79B(H79C,H79D), C80A(H80A,H80B), C80B(H80C,H80D), C81A(H81A,H81B), C81B(H81C,
 H81D), C82A(H82A,H82B), C82B(H82C,H82D), C83A(H83A,H83B), C83B(H83C,H83D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C14(H14), C16(H16), C23(H23), C25(H25), C38(H38),
 C39(H39), C40(H40), C55(H55), C56(H56), C57(H57), C58(H58)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C33A(H33A,H33B,H33C), C33B(H33D,H33E,H33F),
 C34A(H34A,H34B,H34C), C34B(H34D,H34E,H34F), C35A(H35A,H35B,H35C), C35B(H35D,
 H35E,H35F), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C)
;
_shelx_res_checksum              62447
_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 1.955
_oxdiff_exptl_absorpt_empirical_full_min 0.542