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_4133350
_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         'C35 H61 Th, I'
_chemical_formula_sum            'C35 H61 I Th'
_chemical_formula_weight         840.77
_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
_audit_creation_date             2018-10-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.518(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3556(6)
_cell_length_b                   23.2292(17)
_cell_length_c                   16.8874(13)
_cell_measurement_reflns_used    8003
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.0420
_cell_measurement_theta_min      3.7850
_cell_volume                     3536.2(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 0.998
_diffrn_measured_fraction_theta_max 0.978
_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   -106.00 -29.00   1.00    3.00    --  -41.74 -57.00 -90.00   77
  2  \w    -69.00  33.00   1.00    3.00    --  -41.74  77.00  30.00  102
  3  \w     29.00  76.00   1.00    3.00    --   41.74-125.00-180.00   47
  4  \w     35.00 103.00   1.00    7.00    --  107.19 -61.00 -60.00   68
  5  \w    138.00 167.00   1.00    7.00    --  107.19 125.00-150.00   29
  6  \w     98.00 175.00   1.00    7.00    --  107.19  45.00  90.00   77
  7  \w     83.00 109.00   1.00    7.00    --  107.19-125.00-120.00   26
  8  \w     35.00  61.00   1.00    7.00    --  107.19-125.00-120.00   26
  9  \w     86.00 165.00   1.00    7.00    --  107.19  45.00  30.00   79
 10  \w    130.00 177.00   1.00    7.00    --  107.19 125.00  60.00   47
 11  \w     35.00 130.00   1.00    7.00    --  107.19 -61.00 150.00   95
 12  \w    -97.00 -71.00   1.00    4.00    --  -41.74-156.00  54.00   26
 13  \w     49.00  74.00   1.00    4.00    --   41.74 -77.00 150.00   25
 14  \w    -20.00  15.00   1.00    4.00    --   41.74 -77.00 150.00   35
 15  \w     91.00 117.00   1.00    7.00    --  107.19-125.00 -30.00   26
 16  \w    151.00 177.00   1.00    7.00    --  107.19  61.00 120.00   26
 17  \w    124.00 150.00   1.00    7.00    --  107.19 125.00-180.00   26
 18  \w     85.00 111.00   1.00    7.00    --  107.19  61.00 120.00   26
 19  \w     59.00 100.00   1.00    7.00    --  107.19  15.00-150.00   41
;
_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      0.1181551000
_diffrn_orient_matrix_UB_12      0.0198111000
_diffrn_orient_matrix_UB_13      -0.0424356000
_diffrn_orient_matrix_UB_21      -0.0521553000
_diffrn_orient_matrix_UB_22      0.0627215000
_diffrn_orient_matrix_UB_23      0.0021576000
_diffrn_orient_matrix_UB_31      0.1118960000
_diffrn_orient_matrix_UB_32      0.0084322000
_diffrn_orient_matrix_UB_33      0.0846874000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0749
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18439
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.338
_diffrn_reflns_theta_min         3.806
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    20.574
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47136
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.579
_exptl_crystal_description       block
_exptl_crystal_F_000             1656
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.451
_refine_diff_density_min         -2.599
_refine_diff_density_rms         0.221
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         6957
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0229P)^2^+27.5278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0976
_refine_ls_wR_factor_ref         0.1031
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6010
_reflns_number_total             6957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound2
_cod_database_code               4133350
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1I1Th1
_reflns_odcompleteness_completeness 99.83
_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
 Th1-C35 = Th1-C35'
 2.45 with sigma of 0.01
 Th1-I1 = Th1-I1'
 3.05 with sigma of 0.01
 H8A-H35F
 2.2 with sigma of 0.1
 H11C-H35E
 2.2 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C35) \\sim Ueq, Uanis(I1) \\sim Ueq, Uanis(I1') \\sim Ueq: with sigma of
0.0001 and sigma for terminal atoms of 0.0002
Uanis(I1) = Uanis(I1')
Uanis(C35) = Uanis(C35')
4. Others
 Sof(I1')=Sof(C35')=Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(1)
 Sof(I1)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
5.a Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C35'(H35D,H35E,H35F)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C20(H20), C22(H22)
5.c 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)
;
_shelx_res_checksum              82559
_shelx_hkl_checksum              58990
_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 1.753
_oxdiff_exptl_absorpt_empirical_full_min 0.520