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_4133364
_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         'C52 H87 N4 P Th'
_chemical_formula_sum            'C52 H87 N4 P Th'
_chemical_formula_weight         1031.26
_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             2018-10-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                101.751(4)
_cell_angle_beta                 90.019(4)
_cell_angle_gamma                99.921(5)
_cell_formula_units_Z            4
_cell_length_a                   14.5978(8)
_cell_length_b                   18.9744(10)
_cell_length_c                   19.2277(10)
_cell_measurement_reflns_used    9848
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.2400
_cell_measurement_theta_min      3.7910
_cell_volume                     5132.7(5)
_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      100.00(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 0.966
_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   -116.00 -24.00   1.00    1.00    --  -41.49 -37.00   0.00   92
  2  \w    -41.00  -7.00   1.00    1.00    --  -41.49 125.00  90.00   34
  3  \w   -116.00 -17.00   1.00    1.00    --  -41.49 -37.00  90.00   99
  4  \w    -86.00 -54.00   1.00    1.00    --  -41.49 125.00  90.00   32
  5  \w    -86.00 -56.00   1.00    1.00    --  -41.49-164.00 129.00   30
  6  \w      1.00  77.00   1.00    1.00    --   41.49 -99.00 -30.00   76
  7  \w     25.00  63.00   1.00    1.00    --   41.49-125.00 -90.00   38
  8  \w     50.00 107.00   1.00    2.00    --  107.19 -94.00  90.00   57
  9  \w     96.00 159.00   1.00    2.00    --  107.19 125.00  60.00   63
 10  \w     41.00  70.00   1.00    2.00    --  107.19 -61.00  30.00   29
 11  \w     31.00 131.00   1.00    2.00    --  107.19 -30.00 -30.00  100
 12  \w     89.00 178.00   1.00    2.00    --  107.19  30.00 150.00   89
 13  \w    106.00 137.00   1.00    2.00    --  107.19 125.00  90.00   31
 14  \w     47.00  87.00   1.00    2.00    --  107.19-125.00  30.00   40
 15  \w     35.00 121.00   1.00    2.00    --  107.19 -61.00 120.00   86
 16  \w     84.00 121.00   1.00    2.00    --  107.19-125.00-120.00   37
 17  \w     32.00 108.00   1.00    2.00    --  107.19 -94.00 -90.00   76
 18  \w     84.00 111.00   1.00    2.00    --  107.19 -61.00  30.00   27
 19  \w     35.00 116.00   1.00    2.00    --  107.19-125.00  60.00   81
 20  \w     27.00 143.00   1.00    2.00    --  107.19 -15.00 120.00  116
;
_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      0.0512072000
_diffrn_orient_matrix_UB_12      0.0239016000
_diffrn_orient_matrix_UB_13      -0.0636788000
_diffrn_orient_matrix_UB_21      0.0519778000
_diffrn_orient_matrix_UB_22      0.0694511000
_diffrn_orient_matrix_UB_23      0.0499229000
_diffrn_orient_matrix_UB_31      0.0785642000
_diffrn_orient_matrix_UB_32      -0.0412753000
_diffrn_orient_matrix_UB_33      0.0125765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0752
_diffrn_reflns_av_unetI/netI     0.0979
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            37108
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.489
_diffrn_reflns_theta_min         3.562
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.921
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50335
_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            purple
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         12.442
_refine_diff_density_min         -3.700
_refine_diff_density_rms         0.323
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1087
_refine_ls_number_reflns         19960
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1020
_refine_ls_R_factor_gt           0.0842
_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^)+(0.1220P)^2^+115.7599P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2139
_refine_ls_wR_factor_ref         0.2295
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16066
_reflns_number_total             19960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound16
_cod_database_code               4133364
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1P1Th1
_reflns_odcompleteness_completeness 99.91
_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. Restrained distances
 H8C-H12A
 -2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C22) \\sim
Ueq, Uanis(C36) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C56) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(N8) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.01
Uanis(C9) = Uanis(C7)
Uanis(C64) = Uanis(C65)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C20(H20), C22(H22), C37(H37), C39(H39), C55(H55), C57(H57),
 C72(H72), C74(H74), C89(H89), C91(H91)
4.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), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C81(H81A,H81B,
 H81C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,
 H86B,H86C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C),
 C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C), C102(H10D,H10E,
 H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L)
;
_shelx_res_checksum              99297
_shelx_hkl_checksum              69578
_shelx_fab_checksum              57409
_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 3.674
_oxdiff_exptl_absorpt_empirical_full_min 0.380