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_4133357
_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         'C57 H96 N P Th, C3 H3'
_chemical_formula_sum            'C60 H99 N P Th'
_chemical_formula_weight         1097.41
_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             2018-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                78.722(3)
_cell_angle_beta                 85.304(3)
_cell_angle_gamma                76.160(3)
_cell_formula_units_Z            2
_cell_length_a                   10.5187(4)
_cell_length_b                   11.0949(4)
_cell_length_c                   25.1635(9)
_cell_measurement_reflns_used    10651
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.1000
_cell_measurement_theta_min      4.2000
_cell_volume                     2794.46(18)
_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 0.998
_diffrn_measured_fraction_theta_max 0.967
_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  35.00   1.00    1.00    --  -41.62  77.00-120.00   99
  2  \w    -69.00 -42.00   1.00    1.00    --  -41.62  57.00 150.00   27
  3  \w    -69.00  32.00   1.00    1.00    --  -41.62  57.00  30.00  101
  4  \w    -65.00  31.00   1.00    1.00    --  -41.62  37.00-180.00   96
  5  \w     71.00  97.00   1.00    1.00    --   41.62-125.00 -90.00   26
  6  \w     94.00 121.00   1.00    3.00    --  107.19  45.00 150.00   27
  7  \w     38.00 121.00   1.00    3.00    --  107.19-125.00-150.00   83
  8  \w     80.00 178.00   1.00    3.00    --  107.19  30.00 -30.00   98
  9  \w     25.00 106.00   1.00    3.00    --  107.19 -94.00 -90.00   81
 10  \w    101.00 170.00   1.00    3.00    --  107.19 125.00 -30.00   69
 11  \w     65.00 118.00   1.00    3.00    --  107.19-125.00  60.00   53
 12  \w     39.00 122.00   1.00    3.00    --  107.19 -30.00   0.00   83
 13  \w     56.00 140.00   1.00    3.00    --  107.19  15.00 -60.00   84
 14  \w    138.00 163.00   1.00    3.00    --  107.19  45.00 150.00   25
 15  \w     45.00 136.00   1.00    3.00    --  107.19 -61.00-120.00   91
 16  \w     79.00 116.00   1.00    3.00    --  107.19  30.00  60.00   37
 17  \w     48.00 140.00   1.00    3.00    --  107.19 -77.00   0.00   92
;
_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      0.1357220000
_diffrn_orient_matrix_UB_12      -0.0225389000
_diffrn_orient_matrix_UB_13      -0.0293126000
_diffrn_orient_matrix_UB_21      0.0221176000
_diffrn_orient_matrix_UB_22      0.1225825000
_diffrn_orient_matrix_UB_23      0.0137660000
_diffrn_orient_matrix_UB_31      0.0622684000
_diffrn_orient_matrix_UB_32      -0.0749452000
_diffrn_orient_matrix_UB_33      0.0534234000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0660
_diffrn_reflns_av_unetI/netI     0.0857
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            20059
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.438
_diffrn_reflns_theta_min         3.585
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.126
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72656
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1142
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.016
_refine_diff_density_min         -1.844
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         10873
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0196P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9905
_reflns_number_total             10873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound9
_cod_database_code               4133357
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1P1Th1
_reflns_odcompleteness_completeness 99.97
_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), C42(H42), C44(H44), C58(H58), C59(H59),
 C60(H60)
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), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C)
;
_shelx_res_checksum              88691
_shelx_hkl_checksum              40978
_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 1.545
_oxdiff_exptl_absorpt_empirical_full_min 0.566