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_4133362
_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         '1.5(C6 H6), C59 H98 N P Th'
_chemical_formula_sum            'C68 H107 N P Th'
_chemical_formula_weight         1201.55
_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             2018-10-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                77.538(2)
_cell_angle_beta                 83.282(2)
_cell_angle_gamma                75.504(3)
_cell_formula_units_Z            2
_cell_length_a                   10.7690(4)
_cell_length_b                   15.6072(4)
_cell_length_c                   19.4589(5)
_cell_measurement_reflns_used    12558
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.9870
_cell_measurement_theta_min      4.1150
_cell_volume                     3084.95(17)
_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 0.969
_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   -112.00 -14.00   1.00    1.24    --  -41.49 -57.00 150.00   98
  2  \w   -114.00 -17.00   1.00    1.24    --  -41.49 -37.00-120.00   97
  3  \w    -72.00  26.00   1.00    1.24    --  -41.49  77.00  30.00   98
  4  \w     17.00  59.00   1.00    1.24    --   41.49 -99.00  90.00   42
  5  \w     36.00  87.00   1.00    1.24    --   41.49-125.00-120.00   51
  6  \w     31.00 121.00   1.00    3.00    --  107.19 -30.00 -60.00   90
  7  \w     67.00 109.00   1.00    3.00    --  107.19 -94.00-180.00   42
  8  \w     79.00 105.00   1.00    3.00    --  107.19  30.00 -30.00   26
  9  \w     89.00 156.00   1.00    3.00    --  107.19  45.00-120.00   67
 10  \w     41.00 121.00   1.00    3.00    --  107.19-125.00   0.00   80
 11  \w     70.00 118.00   1.00    3.00    --  107.19-125.00-180.00   48
 12  \w     79.00 178.00   1.00    3.00    --  107.19  30.00 120.00   99
 13  \w    144.00 171.00   1.00    3.00    --  107.19 125.00  30.00   27
 14  \w     94.00 161.00   1.00    3.00    --  107.19 125.00 -30.00   67
 15  \w    144.00 178.00   1.00    3.00    --  107.19  30.00 -30.00   34
 16  \w     39.00 135.00   1.00    3.00    --  107.19 -77.00   0.00   96
 17  \w     34.00 114.00   1.00    3.00    --  107.19 -45.00  90.00   80
 18  \w     64.00 131.00   1.00    3.00    --  107.19 -45.00 150.00   67
;
_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      0.0323225000
_diffrn_orient_matrix_UB_12      0.0922081000
_diffrn_orient_matrix_UB_13      -0.0299676000
_diffrn_orient_matrix_UB_21      0.1391426000
_diffrn_orient_matrix_UB_22      -0.0394418000
_diffrn_orient_matrix_UB_23      0.0215188000
_diffrn_orient_matrix_UB_31      0.0390469000
_diffrn_orient_matrix_UB_32      -0.0272606000
_diffrn_orient_matrix_UB_33      -0.0724034000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0892
_diffrn_reflns_av_unetI/netI     0.0998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            22278
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.286
_diffrn_reflns_theta_min         4.127
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.314
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60940
_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    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             1254
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.488
_refine_diff_density_min         -4.490
_refine_diff_density_rms         0.208
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     728
_refine_ls_number_reflns         12012
_refine_ls_number_restraints     371
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0591
_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^)+(0.0879P)^2^+6.5565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1510
_refine_ls_wR_factor_ref         0.1566
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10980
_reflns_number_total             12012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound14
_cod_database_code               4133362
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1P1Th1
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C46, C46'}
3. Restrained distances
 C50-C41 = C50-C52
 1.5 with sigma of 0.005
 C46-C47 = C46-C48 = C46-C49 = C39-C46 = C39-C46'
 1.5 with sigma of 0.005
 C46'-C47' = C46'-C48' = C46'-C49'
 1.5 with sigma of 0.005
 C50-C51 \\sim C50-C52
 with sigma of 0.01
4. Rigid bond restraints
 C60, C61, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C60', C61', C62', C63', C64', C65'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C46, C47, C48, C49, C46', C47', C48', C49'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C60' \\sim C61' \\sim C62' \\sim C63' \\sim C64' \\sim C65': within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C46 \\sim C47 \\sim C48 \\sim C49 \\sim C46' \\sim C47' \\sim C48' \\sim C49':
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C60') \\sim Ueq, Uanis(C61') \\sim Ueq, Uanis(C62') \\sim Ueq,
Uanis(C63') \\sim Ueq, Uanis(C64') \\sim Ueq, Uanis(C65') \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C46') \\sim Ueq, Uanis(C47') \\sim Ueq, Uanis(C48') \\sim Ueq,
Uanis(C49') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) = Uanis(C46')
6. Others
 Sof(C46')=Sof(C47')=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C48')=Sof(H48D)=
 Sof(H48E)=Sof(H48F)=Sof(C49')=Sof(H49D)=Sof(H49E)=Sof(H49F)=1-FVAR(1)
 Sof(C46)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=Sof(H48B)=
 Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=FVAR(1)
 Sof(C60')=Sof(H60')=Sof(C61')=Sof(H61')=Sof(C62')=Sof(H62')=Sof(C63')=
 Sof(H63')=Sof(C64')=Sof(H64')=Sof(C65')=Sof(H65')=1-FVAR(2)
 Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C54(H54)
7.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B)
7.c Me refined with riding coordinates:
 C52(H52A,H52B,H52C)
7.d Aromatic/amide H refined with riding coordinates:
 C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C3(H3), C5(H5),
 C20(H20), C22(H22), C38(H38), C40(H40), C60'(H60'), C61'(H61'), C62'(H62'),
 C63'(H63'), C64'(H64'), C65'(H65'), C66(H66), C67(H67), C68(H68)
7.e Fitted hexagon refined as free rotating group:
 C60(C61,C62,C63,C64,C65), C60'(C61',C62',C63',C64',C65')
7.f 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), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C47'(H47D,H47E,H47F), C48'(H48D,H48E,H48F),
 C49'(H49D,H49E,H49F), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              70783
_shelx_hkl_checksum              17908
_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 1.916
_oxdiff_exptl_absorpt_empirical_full_min 0.578