A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies.
Zhang, Congcong; Hou, Guohua; Zi, Guofu; Ding, Wanjian; Walter, Marc D.; Journal of the American Chemical Society 140 (2018) 14511–14525; doi:10.1021/jacs.8b09746

data_4133361
_publ_section_title
;
 A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis,
 Structure, Reactivity, and Computational Studies.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14511
_journal_page_last               14525
_journal_paper_doi               10.1021/jacs.8b09746
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C56 H96 N P Si Th, 1.5(C6 H6)'
_chemical_formula_sum            'C65 H105 N P Si Th'
_chemical_formula_weight         1191.59
_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             2018-01-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                85.562(4)
_cell_angle_beta                 74.609(5)
_cell_angle_gamma                63.017(6)
_cell_formula_units_Z            2
_cell_length_a                   12.8472(8)
_cell_length_b                   13.0939(7)
_cell_length_c                   21.1147(12)
_cell_measurement_reflns_used    11493
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.9060
_cell_measurement_theta_min      4.0020
_cell_volume                     3047.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3127
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.970
_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    -64.00  30.00   1.00    1.00    --  -39.74  37.00 -30.00   94
  2  \w   -122.00 -36.00   1.00    1.00    --  -39.74 178.00   0.00   86
  3  \w   -110.00 -15.00   1.00    1.00    --  -39.74 -37.00 150.00   95
  4  \w      1.00  55.00   1.00    1.00    --   39.74 -99.00  30.00   54
  5  \w     99.00 128.00   1.00    1.00    --   39.74 178.00   0.00   29
  6  \w     69.00 108.00   1.00    1.00    --   39.74  37.00-120.00   39
  7  \w     49.00 136.00   1.00    1.00    --  107.19 -61.00 -90.00   87
  8  \w     74.00 120.00   1.00    1.00    --  107.19-125.00  60.00   46
  9  \w     31.00 131.00   1.00    1.00    --  107.19 -77.00  60.00  100
 10  \w    132.00 178.00   1.00    1.00    --  107.19  45.00 -60.00   46
 11  \w     82.00 118.00   1.00    1.00    --  107.19-125.00-120.00   36
 12  \w     38.00 133.00   1.00    1.00    --  107.19 -30.00-180.00   95
 13  \w     77.00 131.00   1.00    1.00    --  107.19 -61.00 120.00   54
 14  \w     52.00  78.00   1.00    1.00    --  107.19-125.00-120.00   26
 15  \w     81.00 171.00   1.00    1.00    --  107.19  45.00   0.00   90
 16  \w     42.00  97.00   1.00    1.00    --  107.19 -45.00  60.00   55
 17  \w     99.00 133.00   1.00    1.00    --  107.19 -45.00  60.00   34
 18  \w     41.00 135.00   1.00    1.00    --  107.19 -15.00 -30.00   94
 19  \w     45.00 105.00   1.00    1.00    --  107.19 -94.00 -90.00   60
;
_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      -0.1064934000
_diffrn_orient_matrix_UB_12      0.0335049000
_diffrn_orient_matrix_UB_13      0.0620373000
_diffrn_orient_matrix_UB_21      0.0709736000
_diffrn_orient_matrix_UB_22      0.0298223000
_diffrn_orient_matrix_UB_23      0.0376782000
_diffrn_orient_matrix_UB_31      -0.0550666000
_diffrn_orient_matrix_UB_32      0.1243482000
_diffrn_orient_matrix_UB_33      -0.0217276000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0446
_diffrn_reflns_av_unetI/netI     0.0613
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            21767
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.422
_diffrn_reflns_theta_min         3.793
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.592
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60757
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.298
_exptl_crystal_description       block
_exptl_crystal_F_000             1242
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.198
_refine_diff_density_min         -2.108
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     652
_refine_ls_number_reflns         11889
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+15.4688P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0923
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11127
_reflns_number_total             11889
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound13
_cod_original_cell_volume        3047.9(3)
_cod_database_code               4133361
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1Si1P1Th1
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C20(H20), C22(H22), C41(H41), C43(H43), C57(H57), C58(H58),
 C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C)
;
_shelx_res_checksum              43597
_shelx_hkl_checksum              2189
_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 1.547
_oxdiff_exptl_absorpt_empirical_full_min 0.623