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_1575206
_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         'C110 H164 K6 N6 O4, 2.3[C4H10O]'
_chemical_formula_sum            'C119.2 H187 K6 N6 O6.3'
_chemical_formula_weight         2039.54
_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             2024-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-21 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.0700(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.91762(13)
_cell_length_b                   14.57188(13)
_cell_length_c                   26.4106(2)
_cell_measurement_reflns_used    22872
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.8570
_cell_measurement_theta_min      4.2760
_cell_volume                     6049.33(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.112a 64-bit (release 01-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (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                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -74.00  31.00   1.00    3.00    --  -40.66  84.00  30.00  105
  2  \w     46.00  73.00   1.00    3.00    --   40.66 -84.00 -89.00   27
  3  \w     85.00 130.00   1.00   12.00    --  112.00 -84.00 -89.00   45
  4  \w    101.00 166.00   1.00   12.00    --  112.00  84.00  30.00   65
  5  \w    -86.00  -6.00   1.00    3.00    --  -40.66 125.00 120.00   80
  6  \w      3.00  65.00   1.00    3.00    --   40.66 -38.00-150.00   62
  7  \w    -29.00  -4.00   1.00    3.00    --   40.66 -38.00-150.00   25
  8  \w     23.00  50.00   1.00    3.00    --   40.66  57.00  90.00   27
  9  \w     60.00 112.00   1.00    3.00    --   40.66  57.00  90.00   52
 10  \w     40.00 108.00   1.00   12.00    --  112.00-111.00   0.00   68
 11  \w     29.00  57.00   1.00   12.00    --  112.00 -94.00  90.00   28
 12  \w    121.00 163.00   1.00   12.00    --  112.00  77.00   0.00   42
 13  \w     70.00  95.00   1.00   12.00    --  112.00-111.00 -90.00   25
 14  \w     40.00  66.00   1.00   12.00    --  112.00-111.00 -90.00   26
 15  \w     54.00 138.00   1.00   12.00    --  112.00 -45.00 -90.00   84
 16  \w     82.00 107.00   1.00   12.00    --  112.00 -94.00  90.00   25
 17  \w    103.00 178.00   1.00   12.00    --  112.00  77.00 -30.00   75
 18  \w     33.00 107.00   1.00   12.00    --  112.00 -94.00 150.00   74
 19  \w     56.00  83.00   1.00   12.00    --  112.00 -94.00-180.00   27
 20  \w    108.00 152.00   1.00   12.00    --  112.00  77.00 -90.00   44
 21  \w     40.00 122.00   1.00   12.00    --  112.00 -61.00-150.00   82
 22  \w     64.00  91.00   1.00   12.00    --  112.00-111.00  60.00   27
 23  \w    132.00 178.00   1.00   12.00    --  112.00 111.00-150.00   46
 24  \w     96.00 121.00   1.00   12.00    --  112.00  30.00 -30.00   25
 25  \w    153.00 178.00   1.00   12.00    --  112.00  30.00 -30.00   25
 26  \w     45.00  71.00   1.00   12.00    --  112.00 -94.00 120.00   26
;
_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      0.0602251000
_diffrn_orient_matrix_UB_12      0.0815079000
_diffrn_orient_matrix_UB_13      0.0156577000
_diffrn_orient_matrix_UB_21      0.0293255000
_diffrn_orient_matrix_UB_22      -0.0451647000
_diffrn_orient_matrix_UB_23      0.0525338000
_diffrn_orient_matrix_UB_31      0.0715069000
_diffrn_orient_matrix_UB_32      -0.0500229000
_diffrn_orient_matrix_UB_33      -0.0219852000
_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  0.0261
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            42711
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.924
_diffrn_reflns_theta_min         3.045
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.321
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.371
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (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 yellow'
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2217
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.302
_exptl_crystal_size_min          0.241
_refine_diff_density_max         0.847
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     693
_refine_ls_number_reflns         12452
_refine_ls_number_restraints     300
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0746P)^2^+2.0609P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1244
_refine_ls_wR_factor_ref         0.1278
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11362
_reflns_number_total             12452
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp078
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_original_formula_sum        'C119.20 H187 K6 N6 O6.30'
_cod_database_code               1575206
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C59 H92 N3 O3 K3'
_shelx_estimated_absorpt_t_max   0.605
_shelx_estimated_absorpt_t_min   0.465
_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
 O4-C62 \\sim O4-C61 \\sim O3-C56 \\sim O3-C58
 with sigma of 0.02
 C57-C56 \\sim C62-C63 \\sim C60-C61 \\sim C59-C58
 with sigma of 0.02
 C57-C59 \\sim C63-C60
 with sigma of 0.02
 C62-C61 \\sim C56-C58
 with sigma of 0.02
 O2-C54 \\sim O2-C53 \\sim O1-C50 \\sim O1-C48
 with sigma of 0.02
 C50-C51 \\sim C54-C55 \\sim C52-C53 \\sim C49-C48
 with sigma of 0.02
 C55-C52 \\sim C51-C49
 with sigma of 0.02
 C50-C48 \\sim C54-C53
 with sigma of 0.02
 K2-O1 \\sim K2-O2
 with sigma of 0.02
 K4-O4 \\sim K3-O3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim C50 \\sim C51 \\sim C55 \\sim C54 \\sim O2 \\sim C53 \\sim C52 \\sim
C48 \\sim C49: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C57 \\sim C56 \\sim O3 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim O4 \\sim
C62 \\sim C63 \\sim K4 \\sim K3: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
4. Others
 Sof(K4)=Sof(O4)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C61)=Sof(H61A)=
 Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=
 1-FVAR(1)
 Sof(K3)=Sof(O3)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 FVAR(1)
 Sof(O2)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(2)
 Sof(O1)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45)
5.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C50(H50A,H50B), C53(H53A,H53B), C54(H54A,H54B), C56(H56A,
 H56B), C58(H58A,H58B), C61(H61A,H61B), C62(H62A,H62B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C11(H11), C13(H13), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C63(H63A,H63B,H63C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 190 electrons were 
found in a volume of 960\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.15[C4H10O] per Asymmetric Unit 
which account for 193 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              76241
_shelx_fab_checksum              90643
_olex2_date_sample_data_collection 2024-03-12
_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 1.445
_oxdiff_exptl_absorpt_empirical_full_min 0.608