Reactivity of a Lewis base supported uranium terminal imido metallocene towards small molecules
Li, Tongyu; Wang, Dongwei; Heng, Yi; Hou, Guohua; Zi, Guofu; Walter, Marc D.; Dalton Transactions  (2023) –; doi:10.1039/D3DT02165C

data_7713806
_publ_section_title
;
 Reactivity of a Lewis base supported uranium terminal imido metallocene
 towards small molecules
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02165C
_journal_year                    2023
_chemical_formula_moiety         'C42 H72 N2 Si6 U'
_chemical_formula_sum            'C42 H72 N2 Si6 U'
_chemical_formula_weight         1011.58
_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
_audit_creation_date             2021-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-06-29 deposited with the CCDC.	2023-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                92.121(2)
_cell_angle_beta                 101.119(2)
_cell_angle_gamma                97.782(2)
_cell_formula_units_Z            4
_cell_length_a                   12.0216(4)
_cell_length_b                   22.2346(5)
_cell_length_c                   23.1886(4)
_cell_measurement_reflns_used    26310
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      76.1370
_cell_measurement_theta_min      3.8570
_cell_volume                     6013.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.949
_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     -4.00  27.00   0.50    0.81    --  -46.95  23.00 -17.00   62
  2  \w    -16.00  11.00   0.50    0.81    --  -46.95  19.00 120.00   54
  3  \w    -68.00 -35.00   0.50    1.00    -- -102.00  61.00 120.00   66
  4  \w    -57.00 -31.00   0.50    1.00    -- -102.00 125.00  30.00   52
  5  \w    -69.00 -29.00   0.50    1.00    -- -102.00  61.00-120.00   80
  6  \w   -111.00 -70.00   0.50    1.00    -- -102.00 125.00  30.00   82
  7  \w   -115.00 -70.00   0.50    1.00    -- -102.00 132.00  27.74   90
  8  \w   -108.00 -35.00   0.50    0.81    --  -46.95 -23.00 177.00  146
  9  \w    -24.00  30.00   0.50    0.81    --   46.95 -23.00 177.00  108
 10  \w    -26.00  42.00   0.50    0.81    --   46.95 -37.00 120.00  136
 11  \w     42.00 116.00   0.50    0.81    --   46.95  23.00 -17.00  148
 12  \w     96.00 177.00   0.50    1.00    --  104.75  23.00 -17.00  162
 13  \w    123.00 152.00   0.50    1.00    --  104.75  15.00  90.00   58
 14  \w    125.00 156.00   0.50    1.00    --  104.75  15.00  60.00   62
 15  \w     76.00 170.00   0.50    1.00    --  104.75 125.00 -30.00  188
 16  \w    142.00 176.00   0.50    1.00    --  104.75 125.00   0.00   68
 17  \w    137.00 164.00   0.50    1.00    --  104.75 125.00-120.00   54
 18  \w    136.00 177.00   0.50    1.00    --  104.75  45.00-180.00   82
 19  \w     83.00 136.00   0.50    1.00    --  104.75 125.00   0.00  106
 20  \w     77.00 127.00   0.50    1.00    --  104.75 125.00-120.00  100
 21  \w     92.00 132.00   0.50    1.00    --  104.75  45.00-180.00   80
 22  \w     45.00  70.00   0.50    0.81    --   46.95  37.00-120.00   50
 23  \w     32.00  72.00   0.50    1.00    --  104.75 -61.00   0.00   80
 24  \w     33.00  73.00   0.50    1.00    --  104.75 -61.00  30.00   80
 25  \w     38.00  77.00   0.50    1.00    --  104.75 -77.00   0.00   78
 26  \w     80.00 116.00   0.50    1.00    --  104.75-125.00   0.00   72
 27  \w     76.00 112.00   0.50    1.00    --  104.75-125.00 -30.00   72
 28  \w     57.00 114.00   0.50    1.00    --  104.75-125.00-150.00  114
 29  \w     32.00 117.00   0.50    1.00    --  104.75-125.00 -60.00  170
 30  \w     41.00  80.00   0.50    1.00    --  104.75 -94.00-180.00   78
 31  \w     36.00  63.00   0.50    1.00    --  104.75 -61.00-150.00   54
 32  \w     33.00 108.00   0.50    1.00    --  104.75 -77.00 -90.00  150
 33  \w     30.00  94.00   0.50    0.81    --   46.95-125.00  30.00  128
 34  \w     34.00  62.00   0.50    1.00    --  104.75 -61.00 120.00   56
 35  \w     33.00  73.00   0.50    1.00    --  104.75 -61.00  90.00   80
 36  \w     33.00 115.00   0.50    1.00    --  104.75-125.00 150.00  164
 37  \w     33.00  91.00   0.50    1.00    --  104.75 -77.00 -30.00  116
 38  \w     34.00  59.00   0.50    1.00    --  104.75 -61.00 -30.00   50
 39  \w    -24.00  62.00   0.50    0.81    --   46.95 -57.00-120.00  172
 40  \w   -119.00 -75.00   0.50    0.81    --  -46.95-125.00 -90.00   88
 41  \w   -173.00 -94.00   0.50    1.00    -- -102.00 -45.00 -60.00  158
 42  \w   -171.00-124.00   0.50    1.00    -- -102.00 -45.00 150.00   94
 43  \w   -175.00-116.00   0.50    1.00    -- -102.00 -23.00 177.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0681480000
_diffrn_orient_matrix_UB_12      -0.0631711000
_diffrn_orient_matrix_UB_13      0.0035189000
_diffrn_orient_matrix_UB_21      0.1130022000
_diffrn_orient_matrix_UB_22      -0.0257169000
_diffrn_orient_matrix_UB_23      0.0198922000
_diffrn_orient_matrix_UB_31      -0.0033681000
_diffrn_orient_matrix_UB_32      0.0160956000
_diffrn_orient_matrix_UB_33      0.0647733000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0828
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            24360
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.868
_diffrn_reflns_theta_min         3.788
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.913
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52301
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.117
_exptl_crystal_description       block
_exptl_crystal_F_000             2056
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         8.297
_refine_diff_density_min         -4.498
_refine_diff_density_rms         0.321
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     959
_refine_ls_number_reflns         24360
_refine_ls_number_restraints     504
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1225
_refine_ls_R_factor_gt           0.1078
_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^)+(0.1384P)^2^+188.7739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2886
_refine_ls_wR_factor_ref         0.3025
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19525
_reflns_number_total             24360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02165c2.cif
_cod_data_source_block           compound16
_cod_database_code               7713806
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1Si1U1
_shelx_estimated_absorpt_t_max   0.469
_shelx_estimated_absorpt_t_min   0.214
_diffrn_oxdiff_digest_frames
;
0157bc883dc99d20d394b0aeb8f1d3d0f604206d0ae
;
_diffrn_oxdiff_digest_hkl
;
0113b289d280dad36b2f1ba95781e3cfb7b0dd
;
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.806(3)
 0.194(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq,
Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq,
Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4.a Me refined with riding coordinates:
 C10(H10A,H10B,H10C)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C17(H17), C19(H19), C30(H30), C31(H31), C33(H33), C34(H34),
 C37(H37), C38(H38), C40(H40), C41(H41), C45(H45), C47(H47), C59(H59), C61(H61),
  C72(H72), C73(H73), C75(H75), C76(H76), C79(H79), C80(H80), C82(H82), C83(H83)
4.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,
 H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C42(H42A,H42B,H42C),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C77(H77A,
 H77B,H77C), C84(H84A,H84B,H84C)
;
_shelx_res_checksum              52999
_shelx_fab_checksum              84553
_platon_squeeze_void_probe_radius 1.20
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.644
_oxdiff_exptl_absorpt_empirical_full_min 0.617