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_1575208
_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         'C118 H176 Cl3 K3 N6 O6 U2, C4 H10 O'
_chemical_formula_sum            'C122 H186 Cl3 K3 N6 O7 U2'
_chemical_formula_weight         2548.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-04-01
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-08 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.3155(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.70041(19)
_cell_length_b                   22.5404(3)
_cell_length_c                   26.0053(3)
_cell_measurement_reflns_used    47425
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.8000
_cell_measurement_theta_min      2.6520
_cell_volume                     12396.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.101a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.100a 64-bit (release 20-03-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.101a (Rigaku OD, 2025)'
_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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     39.00  64.00   0.50    1.10    --   66.03-137.00-139.00   50
  2  \w     37.00  62.00   0.50    1.10    --   66.03-133.00  38.00   50
  3  \w    -64.00 -39.00   0.50    1.10    --  -66.72 137.00 -76.00   50
  4  \w    -78.00 -53.00   0.50    1.10    --  -66.72 133.00 106.00   50
  5  \w   -101.00 -43.00   0.50    1.10    --  -69.30 133.00 106.00  116
  6  \w    -90.00 -65.00   0.50    1.10    --  -69.30 137.00 -76.00   50
  7  \w     48.00  73.00   0.50    1.10    --   69.55-133.00  38.00   50
  8  \w     42.00  67.00   0.50    1.10    --   69.55-137.00-139.00   50
  9  \w     84.00 113.00   0.50    1.10    --   77.95-137.00-139.00   58
 10  \w     72.00  98.00   0.50    1.10    --   77.95-133.00  38.00   52
 11  \w     73.00 119.00   0.50    1.10    --   77.95 137.00 -76.00   92
 12  \w     75.00 119.00   0.50    1.10    --   77.95 133.00 106.00   88
 13  \w     33.00  73.00   0.50    1.10    --   66.03 -95.00  90.00   80
 14  \w     28.00  72.00   0.50    1.10    --   66.03 -95.00 150.00   88
 15  \w     29.00  61.00   0.50    1.10    --   66.03 -95.00 120.00   64
 16  \w     29.00  75.00   0.50    1.10    --   66.03 -95.00  30.00   92
 17  \w    -62.00 -35.00   0.50    1.10    --  -66.72   0.00-120.00   54
 18  \w    -72.00 -39.00   0.50    1.10    --  -66.72   0.00  60.00   66
 19  \w    -69.00 -29.00   0.50    1.10    --  -66.72   0.00  90.00   80
 20  \w    -72.00 -47.00   0.50    1.10    --  -66.72   0.00   0.00   50
 21  \w    -91.00 -26.00   0.50    1.10    --  -66.72 125.00-150.00  130
 22  \w   -101.00 -73.00   0.50    1.10    --  -69.30 -15.00-120.00   56
 23  \w    -77.00 -29.00   0.50    1.10    --  -69.30 125.00 150.00   96
 24  \w    -68.00 -33.00   0.50    1.10    --  -69.30   0.00-120.00   70
 25  \w    -67.00 -35.00   0.50    1.10    --  -69.30   0.00 120.00   64
 26  \w    -71.00 -40.00   0.50    1.10    --  -69.30   0.00  30.00   62
 27  \w    -70.00 -43.00   0.50    1.10    --  -69.30   0.00   0.00   54
 28  \w    -99.00 -39.00   0.50    1.10    --  -69.30 -15.00-180.00  120
 29  \w     62.00  97.00   0.50    1.10    --   69.55  15.00 150.00   70
 30  \w     37.00  94.00   0.50    1.10    --   69.55-125.00  90.00  114
 31  \w     29.00  80.00   0.50    1.10    --   69.55-125.00   0.00  102
 32  \w     33.00  76.00   0.50    1.10    --   69.55 -95.00-150.00   86
 33  \w     32.00  60.00   0.50    1.10    --   69.55 -95.00 -60.00   56
 34  \w    -73.00 -33.00   0.50    1.10    --  -74.82 140.00  71.89   80
 35  \w   -110.00 -81.00   0.50    1.10    --  -74.82 140.00  71.89   58
 36  \w   -112.00 -36.00   0.50    1.10    --  -74.82 143.00 -52.04  152
 37  \w   -112.00 -82.00   0.50    1.10    --  -74.82 141.00 147.74   60
 38  \w    -68.00 -43.00   0.50    1.10    --  -74.82 139.00 -94.85   50
 39  \w   -110.00 -80.00   0.50    1.10    --  -74.82 139.00 -94.85   60
 40  \w     44.00 105.00   0.50    1.10    --   77.95-125.00 -90.00  122
 41  \w     38.00 105.00   0.50    1.10    --   77.95-125.00 -30.00  134
 42  \w     40.00  65.00   0.50    1.10    --   77.95 -95.00-120.00   50
 43  \w     42.00 104.00   0.50    1.10    --   77.95-125.00 150.00  124
 44  \w     80.00 105.00   0.50    1.10    --   77.95-125.00  90.00   50
 45  \w     50.00  75.00   0.50    1.10    --   77.95 -95.00 -90.00   50
 46  \w     46.00  72.00   0.50    1.10    --   77.95-125.00  90.00   52
 47  \w     57.00 118.00   0.50    1.10    --   77.95  15.00 -90.00  122
 48  \w     80.00 105.00   0.50    1.10    --   77.95-125.00  30.00   50
 49  \w     50.00 109.00   0.50    1.10    --   77.95  15.00  90.00  118
 50  \w     80.00 105.00   0.50    1.10    --   77.95-125.00 120.00   50
 51  \w     61.00 121.00   0.50    1.10    --   77.95  15.00 -30.00  120
 52  \w     50.00  75.00   0.50    1.10    --   77.95 -95.00   0.00   50
 53  \w     40.00  65.00   0.50    1.10    --   77.95 -95.00  60.00   50
 54  \w     78.00 103.00   0.50    1.10    --   77.95-125.00-150.00   50
 55  \w     48.00 120.00   0.50    1.10    --   77.95  15.00 150.00  144
;
_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      0.0021570000
_diffrn_orient_matrix_UB_12      0.0212105000
_diffrn_orient_matrix_UB_13      -0.0556516000
_diffrn_orient_matrix_UB_21      0.0002989000
_diffrn_orient_matrix_UB_22      0.0649969000
_diffrn_orient_matrix_UB_23      0.0184510000
_diffrn_orient_matrix_UB_31      0.0727453000
_diffrn_orient_matrix_UB_32      -0.0008384000
_diffrn_orient_matrix_UB_33      0.0246946000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            103540
_diffrn_reflns_point_group_measured_fraction_full 0.788
_diffrn_reflns_point_group_measured_fraction_max 0.788
_diffrn_reflns_theta_full        66.588
_diffrn_reflns_theta_max         66.588
_diffrn_reflns_theta_min         2.678
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.202
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.346
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.101a (Rigaku Oxford Diffraction, 2025)
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            'lustrous dark black'
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5232
_exptl_crystal_size_max          0.302
_exptl_crystal_size_mid          0.115
_exptl_crystal_size_min          0.065
_refine_diff_density_max         2.718
_refine_diff_density_min         -2.147
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.492(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1422
_refine_ls_number_reflns         17248
_refine_ls_number_restraints     1925
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0478
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1233
_refine_ls_wR_factor_ref         0.1269
_reflns_Friedel_coverage         0.581
_reflns_Friedel_fraction_full    0.580
_reflns_Friedel_fraction_max     0.580
_reflns_number_gt                15529
_reflns_number_total             17248
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           yp278
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_original_cell_volume        12396.0(3)
_cod_database_code               1575208
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C122 H186 N6 O7 Cl3 K3 U2'
_shelx_estimated_absorpt_t_max   0.586
_shelx_estimated_absorpt_t_min   0.168
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.508(7)
 0.492(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C71-C60 \\sim C75-C60
 with sigma of 0.02
 C73-C71 \\sim C74-C71 \\sim C72-C71 \\sim C75-C77 \\sim C75-C76 \\sim C78-C75
 with sigma of 0.02
 C73-C72 \\sim C72-C74 \\sim C73-C74
 with sigma of 0.02
 C78-C77 \\sim C77-C76 \\sim C76-C78
 with sigma of 0.02
 C53-C57 \\sim C56-C57 \\sim C52-C53 \\sim C55-C56 \\sim C54-C55 \\sim C52-C51
 with sigma of 0.02
 O1-C57 \\sim O1-C51 \\sim O1-C54
 with sigma of 0.02
 C15-C14 \\sim C18-C14 \\sim C20-C14 \\sim C17-C14 \\sim C16-C14 \\sim C19-C14
 with sigma of 0.02
 C16-C15 \\sim C15-C17 \\sim C16-C17
 with sigma of 0.02
 C19-C18 \\sim C18-C20 \\sim C20-C19
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O1 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C56 \\sim C57 \\sim C71 \\sim C72 \\sim
C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(O6) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C127)
\\sim Ueq, Uanis(C128) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C75)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=
 Sof(H77C)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=1-FVAR(1)
 Sof(C71)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C73)=Sof(H73A)=Sof(H73B)=
 Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=FVAR(1)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=
 Sof(H56B)=Sof(H57C)=Sof(H57D)=1-FVAR(2)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H57A)=Sof(H57B)=FVAR(2)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(3)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C33(H33), C36(H36), C45(H45), C48(H48), C91(H91), C94(H94), C103(H103),
 C106(H106)
7.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,
 H55B), C56(H56A,H56B), C57(H57A,H57B), C57(H57C,H57D), C109(H10M,H10N),
 C110(H11A,H11B), C111(H11C,H11D), C112(H11E,H11F), C113(H11G,H11H), C115(H11L,
 H11M), C117(H11Q,H11R), C118(H11S,H11T), C119(H11U,H11V), C120(H12A,H12B),
 C121(H12C,H12D), C123(H12H,H12I), C125(H12M,H12N), C126(H12O,H12P), C127(H12Q,
 H12R), C128(H12S,H12T), C133(H13A,H13B), C135(H13F,H13G)
7.c Me refined with riding coordinates:
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C96(H96A,H96B,H96C), C134(H13C,H13D,
 H13E)
7.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C9(H9), C11(H11), C29(H29), C30(H30), C31(H31), C41(H41),
 C42(H42), C43(H43), C59(H59), C61(H61), C66(H66), C68(H68), C87(H87), C88(H88),
  C89(H89), C99(H99), C100(H100), C101(H101)
7.e 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), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C),
 C76(H76A,H76B,H76C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C82(H82A,H82B,
 H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C92(H92A,H92B,H92C), C93(H93A,
 H93B,H93C), C95(H95A,H95B,H95C), C104(H10A,H10B,H10C), C105(H10D,H10E,H10F),
 C107(H10G,H10H,H10I), C108(H10J,H10K,H10L), C114(H11I,H11J,H11K), C116(H11N,
 H11O,H11P), C122(H12E,H12F,H12G), C124(H12J,H12K,H12L), C136(H13H,H13I,H13J)
;
_shelx_res_checksum              84127
_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 4.270
_oxdiff_exptl_absorpt_empirical_full_min 0.592