Fragmentation, catenation, and direct functionalisation of white phosphorus by a uranium(IV)-silyl-phosphino-carbene complex.
Boronski, Josef T.; Seed, John A.; Wooles, Ashley J.; Liddle, Stephen T.; Chemical communications (Cambridge, England) 57 (2021) 5090–5093; doi:10.1039/d1cc01741a

data_7128207
_publ_section_title
;
 Fragmentation, catenation, and direct functionalisation of white
 phosphorus by a uranium(IV)-silyl-phosphino-carbene complex.
;
_journal_issue                   41
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              5090
_journal_page_last               5093
_journal_paper_doi               10.1039/d1cc01741a
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C37 H54 Cl3 Li N4 P2 Si2 U'
_chemical_formula_sum            'C37 H54 Cl3 Li N4 P2 Si2 U'
_chemical_formula_weight         1024.28
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_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   difmap
_audit_creation_date             2020-05-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-03 deposited with the CCDC.	2021-04-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0428(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.67099(17)
_cell_length_b                   21.4630(2)
_cell_length_c                   16.66143(17)
_cell_measurement_reflns_used    12151
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      70.6070
_cell_measurement_theta_min      2.0720
_cell_volume                     4524.81(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.932
_diffrn_measured_fraction_theta_max 0.913
_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    -85.00 -29.00   0.50    0.50    --    0.00  20.00  30.00  112
  2  \w     -3.00  59.00   0.50    0.50    --    0.00  20.00  30.00  124
  3  \w    -34.00  48.00   0.50    0.50    --   55.00  50.00  60.00  164
  4  \w    -33.00  88.00   0.50    0.50    --   55.00  50.00  30.00  242
  5  \w    -34.00  86.00   0.50    0.50    --   55.00  50.00 -30.00  240
  6  \w    115.00 143.00   0.50    0.50    --   55.00  50.00  60.00   56
  7  \w     88.00 143.00   0.50    0.50    --   55.00  50.00 120.00  110
  8  \w     78.00 144.00   0.50    0.50    --   55.00  50.00   0.00  132
  9  \w    110.00 198.00   0.50    0.50    --  110.00  40.00  90.00  176
 10  \w     44.00  70.00   0.50    0.50    --  110.00  40.00 -30.00   52
 11  \w    128.00 198.00   0.50    0.50    --  110.00  40.00  60.00  140
 12  \w     93.00 199.00   0.50    0.50    --  110.00  40.00 -30.00  212
 13  \w    140.00 192.00   0.50    0.50    --  110.00  40.00 120.00  104
 14  \w     21.00 196.00   0.50    0.50    --  110.00   0.00-180.00  350
 15  \w    136.00 166.00   0.50    0.50    --  110.00  40.00  30.00   60
 16  \w     40.00  66.00   0.50    0.50    --  110.00  40.00  30.00   52
 17  \w     96.00 198.00   0.50    0.50    --  110.00  40.00   0.00  204
 18  \w     25.00 123.00   0.50    0.50    --  110.00  40.00 120.00  196
 19  \w     32.00  57.00   0.50    0.50    --  110.00  40.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0335868000
_diffrn_orient_matrix_UB_12      -0.0537875000
_diffrn_orient_matrix_UB_13      0.0544674000
_diffrn_orient_matrix_UB_21      -0.0233157000
_diffrn_orient_matrix_UB_22      0.0472172000
_diffrn_orient_matrix_UB_23      0.0665650000
_diffrn_orient_matrix_UB_31      -0.1144407000
_diffrn_orient_matrix_UB_32      0.0060161000
_diffrn_orient_matrix_UB_33      -0.0345714000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0580
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.932
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22617
_diffrn_reflns_point_group_measured_fraction_full 0.932
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.783
_diffrn_reflns_theta_min         3.361
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    13.126
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.102
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       block
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.533
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.109
_refine_diff_density_max         3.283
_refine_diff_density_min         -2.436
_refine_diff_density_rms         0.179
_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     510
_refine_ls_number_reflns         7969
_refine_ls_number_restraints     247
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0453
_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^)+(0.1016P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1223
_refine_ls_wR_factor_ref         0.1240
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7425
_reflns_number_total             7969
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01741a2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7128206--7128208.cif.'
_cod_original_cell_volume        4524.80(9)
_cod_database_code               7128207
_manchester_internal_diff_code   LSTL186
_manchester_internal_stl_name    UJB16
_manchester_internal_coll_client JB
_manchester_internal_coll_date   08/08/2018
_manchester_internal_process_date 08/08/2018
_manchester_internal_process_user JB
_manchester_internal_solution_date 01/05/2020
_manchester_internal_solution_user JB
_manchester_internal_refinement_date 01/05/2020
_manchester_internal_refinement_user AW
_manchester_internal_validation_date 01/05/2020
_manchester_internal_validation_user AW
_manchester_internal_archive_date 01/05/2020
_manchester_internal_archive_user AW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C37H54Si2N2P2UCl3Li
_chemical_oxdiff_usercomment     JB
_shelx_estimated_absorpt_t_max   0.329
_shelx_estimated_absorpt_t_min   0.054
_reflns_odcompleteness_completeness 92.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 N4-C37A = N4-C37 = N4-C36 = N4-C36A = N4-C35 = N4-C35A = N3-C32A = N3-C32 =
 N3-C33A = N3-C33 = N3-C34A = N3-C34
 1.45 with sigma of 0.01
 C35A-C34A = C34-C35
 1.55 with sigma of 0.01
 C34A-C32A \\sim C34A-C33A \\sim C36A-C35A \\sim C35A-C37A \\sim C35-C37 \\sim
C36-C35 \\sim C34-C32 ~
 C33-C34
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N3 \\sim N4 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim
C32A \\sim C33A \\sim C34A \\sim C35A \\sim C36A \\sim C37A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 N3, N4, C32, C33, C34, C35, C36, C37, C32A, C33A, C34A, C35A, C36A, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=Sof(H35D)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=1-FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C34A(H34C,H34D), C35A(H35C,H35D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25),
  C26(H26), C27(H27), C28(H28)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C32A(H32D,H32E,H32F),
 C33A(H33D,H33E,H33F), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F)
;
_shelx_res_checksum              80698
_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 4.223
_oxdiff_exptl_absorpt_empirical_full_min 0.433