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_7128206
_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         'C32 H38 P7 Si2, C12 H32 Li N4'
_chemical_formula_sum            'C44 H70 Li N4 P7 Si2'
_chemical_formula_weight         934.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-01-09
_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                 91.875(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9343(4)
_cell_length_b                   23.4616(11)
_cell_length_c                   22.0737(12)
_cell_measurement_reflns_used    5152
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.0160
_cell_measurement_theta_min      2.7610
_cell_volume                     5142.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.962
_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     59.00 108.00   0.50    4.00    --   44.70  12.00 -85.00   98
  2  \w    -18.00  20.00   0.50    4.00    --   44.70  12.00 -85.00   76
  3  \w     36.00 132.00   0.50    4.00    --   44.70  60.00 150.00  192
  4  \w    -42.00 131.00   0.50    4.00    --   44.70  20.00  90.00  346
  5  \w     95.00 197.00   0.50   20.00    --  108.20  50.00  60.00  204
  6  \w    139.00 167.00   0.50   20.00    --  108.20  30.00  60.00   56
  7  \w     20.00 197.00   0.50   20.00    --  108.20  50.00-150.00  354
  8  \w     39.00  66.00   0.50   20.00    --  108.20  50.00  90.00   54
  9  \w     73.00 129.00   0.50   20.00    --  108.20  50.00 150.00  112
 10  \w     87.00 192.00   0.50   20.00    --  108.20  50.00  90.00  210
 11  \w    136.00 164.00   0.50   20.00    --  108.20  50.00 150.00   56
 12  \w     26.00  68.00   0.50   20.00    --  108.20  30.00  60.00   84
 13  \w     40.00  67.00   0.50   20.00    --  108.20  50.00  60.00   54
 14  \w    154.00 182.00   0.50   20.00    --  108.20  50.00 120.00   56
 15  \w     22.00 191.00   0.50   20.00    --  108.20  12.00 -85.00  338
;
_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      -0.0836907000
_diffrn_orient_matrix_UB_12      0.0141285000
_diffrn_orient_matrix_UB_13      -0.0580428000
_diffrn_orient_matrix_UB_21      -0.1291259000
_diffrn_orient_matrix_UB_22      0.0008239000
_diffrn_orient_matrix_UB_23      0.0368294000
_diffrn_orient_matrix_UB_31      0.0200017000
_diffrn_orient_matrix_UB_32      0.0641123000
_diffrn_orient_matrix_UB_33      0.0122848000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0870
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            35902
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.690
_diffrn_reflns_theta_min         2.749
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.940
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.949
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
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 reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       plate
_exptl_crystal_F_000             1992
_exptl_crystal_size_max          0.088
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.072
_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     690
_refine_ls_number_reflns         10426
_refine_ls_number_restraints     935
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0686
_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^)+(0.1004P)^2^+2.8744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1798
_refine_ls_wR_factor_ref         0.2010
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7191
_reflns_number_total             10426
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01741a2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7128206--7128208.cif.'
_cod_database_code               7128206
_manchester_internal_diff_code   LSTL226
_manchester_internal_stl_name    UJB29
_manchester_internal_coll_client JB
_manchester_internal_coll_date   08/01/2019
_manchester_internal_process_date 09/01/2019
_manchester_internal_process_user JB
_manchester_internal_solution_date 09/01/2019
_manchester_internal_solution_user JB
_manchester_internal_refinement_date 09/01/2019
_manchester_internal_refinement_user JB/AW
_manchester_internal_validation_date 09/01/2019
_manchester_internal_validation_user JB/AW
_manchester_internal_archive_date 09/01/2019
_manchester_internal_archive_user AW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C44H66LiN4P7Si2
_chemical_oxdiff_usercomment     jb
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.782
_reflns_odcompleteness_completeness 99.50
_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
 N7-C52 = N7-C51 = N7-C53 = N8-C54 = N8-C55 = N8-C56 = N6-C50 = N6-C48 = N6-
 C49 = N5-C46 = N5-C45 = N1-C34 = N1-C33 = N1-C35 = N2-C36 = N2-C37 = N2-C38 =
 N3-C40 = N3-C41 = N3-C39 = N4-C42 = N4-C44 = N4-C43
 1.45 with sigma of 0.01
 C47-C48 = C54-C53 = C36-C35 = C42-C41
 1.55 with sigma of 0.01
 N6-Li1 \\sim N5-Li1 \\sim N8-Li1 \\sim N7-Li1 \\sim N2-Li1 \\sim N3-Li1 \\sim
N1-Li1 \\sim N4-Li1
 with sigma of 0.02
 C52-C53 \\sim C53-C51 \\sim C55-C54 \\sim C54-C56 \\sim C49-C48 \\sim C48-C50
\\sim C46-C47 \\sim C47-C45
 \\sim C39-C41 \\sim C41-C40 \\sim C43-C42 \\sim C42-C44 \\sim C38-C36 \\sim
C36-C37 \\sim C33-C35 \\sim C35-C34
 with sigma of 0.02
 C45-C46 \\sim C55-C56 \\sim C52-C51 \\sim C49-C50 \\sim C38-C37 \\sim C39-C40
\\sim C43-C44 \\sim C33-C34
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Li1 \\sim N1 \\sim N2 \\sim N3 \\sim N4 \\sim C33 \\sim C34 \\sim C35 \\sim C36
\\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44
\\sim N7 \\sim N5 \\sim N6 \\sim N8 \\sim C45 \\sim C46 \\sim C47 \\sim C48
\\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Li1, N1, N2, N3, N4, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43,
 C44, N7, N5, N6, N8, C45, C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N7)=Sof(N5)=Sof(N6)=Sof(N8)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=
 Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=
 Sof(H50B)=Sof(H50C)=Sof(C51)=Sof(H51B)=Sof(H51A)=Sof(H51C)=Sof(C52)=Sof(H52A)=
 Sof(H52C)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 1-FVAR(1)
 Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B), C41(H41A,H41B), C42(H42A,H42B), C47(H47A,
 H47B), C48(H48A,H48B), C53(H53A,H53B), C54(H54A,H54B)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C37(H37A,
 H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51B,H51A,H51C), C52(H52A,
 H52C,H52B), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              68479
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.573
_oxdiff_exptl_absorpt_empirical_full_min 0.549