The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium(iv) and uranium(iv) alkyls
Gardner, Benedict M.; Cleaves, Peter A.; Kefalidis, Christos E.; Fang, Jian; Maron, Laurent; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Chemical Science 5 (2014) 2489–; doi:10.1039/c4sc00182f

data_1515379
_publ_section_title
;
 The role of 5f-orbital participation in unexpected inversion of the
 \s-bond metathesis reactivity trend of triamidoamine thorium(iv) and
 uranium(iv) alkyls
;
_journal_issue                   6
_journal_name_full               'Chemical Science'
_journal_page_first              2489
_journal_paper_doi               10.1039/c4sc00182f
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C33 H75 Cl N4 Si3 Th'
_chemical_formula_sum            'C33 H75 Cl N4 Si3 Th'
_chemical_formula_weight         879.73
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.515(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.004(2)
_cell_length_b                   15.655(2)
_cell_length_c                   20.436(3)
_cell_measurement_reflns_used    10810
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.288
_cell_measurement_theta_min      2.260
_cell_volume                     4160.1(10)
_computing_cell_refinement       'Bruker SAINT version 6.36A (Bruker, 2002)'
_computing_data_collection       'Bruker SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'Bruker SAINT; SHELXTL (Sheldrick, 2008)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      90.15
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25312
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.356
_diffrn_reflns_theta_min         2.036
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.761
_exptl_absorpt_correction_T_max  0.4305
_exptl_absorpt_correction_T_min  0.3468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2007/2 (Bruker,2007) was used for absorption correction.
wR2(int) was 0.0676 before and 0.0374 after correction.
The Ratio of minimum to maximum transmission is 0.8056.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             1800
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.38
_refine_diff_density_max         3.285
_refine_diff_density_min         -1.872
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         9269
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0601P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7830
_reflns_number_total             9269
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc00182f2.cif
_cod_data_source_block           1b
_cod_depositor_comments
'Adding full bibliography for 1515379--1515382.cif.'
_cod_original_cell_volume        4159.9(11)
_cod_database_code               1515379
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1(0.027) H2A(0.043) H2B(0.043) H2C(0.043) H3A(0.051) H3B(0.051)
 H3C(0.051) H4(0.026) H5A(0.042) H5B(0.042) H5C(0.042) H6A(0.04) H6B(0.04)
 H6C(0.04) H7(0.026) H8A(0.05) H8B(0.05) H8C(0.05) H9A(0.04) H9B(0.04)
 H9C(0.04) H10A(0.024) H10B(0.024) H11A(0.023) H11B(0.023) H12(0.033)
 H13A(0.058) H13B(0.058) H13C(0.058) H14A(0.08) H14B(0.08) H14C(0.08)
 H15(0.029) H16A(0.065) H16B(0.065) H16C(0.065) H17A(0.078) H17B(0.078)
 H17C(0.078) H18(0.033) H19A(0.05) H19B(0.05) H19C(0.05) H20A(0.059)
 H20B(0.059) H20C(0.059) H21A(0.024) H21B(0.024) H22A(0.022) H22B(0.022)
 H23(0.032) H24A(0.061) H24B(0.061) H24C(0.061) H25A(0.046) H25B(0.046)
 H25C(0.046) H26(0.029) H27A(0.045) H27B(0.045) H27C(0.045) H28A(0.051)
 H28B(0.051) H28C(0.051) H29(0.029) H30A(0.038) H30B(0.038) H30C(0.038)
 H31A(0.058) H31B(0.058) H31C(0.058) H32A(0.022) H32B(0.022) H33A(0.022)
 H33B(0.022)
 Fixed X: H1(1.2872) H2A(1.1362) H2B(1.2316) H2C(1.1436) H3A(1.2754)
 H3B(1.3607) H3C(1.3582) H4(1.2823) H5A(1.2787) H5B(1.3592) H5C(1.3604)
 H6A(1.1313) H6B(1.2307) H6C(1.1465) H7(1.0256) H8A(1.166) H8B(1.1153)
 H8C(1.2187) H9A(1.1119) H9B(1.0115) H9C(1.0096) H10A(1.1613) H10B(1.0509)
 H11A(1.075) H11B(1.0955) H12(0.7818) H13A(0.7018) H13B(0.6384) H13C(0.5981)
 H14A(0.5942) H14B(0.6473) H14C(0.6983) H15(0.7166) H16A(0.5736) H16B(0.561)
 H16C(0.6543) H17A(0.6532) H17B(0.5655) H17C(0.5669) H18(0.8043) H19A(0.9095)
 H19B(0.9749) H19C(0.9887) H20A(0.9467) H20B(0.9355) H20C(0.8432) H21A(0.9064)
 H21B(0.9981) H22A(0.9693) H22B(0.8501) H23(0.5642) H24A(0.6019) H24B(0.4919)
 H24C(0.5878) H25A(0.5569) H25B(0.4675) H25C(0.5687) H26(0.7472) H27A(0.8822)
 H27B(0.882) H27C(0.9174) H28A(0.6137) H28B(0.7015) H28C(0.69) H29(0.7694)
 H30A(0.9393) H30B(0.9324) H30C(0.9403) H31A(0.7783) H31B(0.7765) H31C(0.6774)
 H32A(0.7373) H32B(0.7452) H33A(0.8777) H33B(0.9217)
 Fixed Y: H1(0.7021) H2A(0.6749) H2B(0.6188) H2C(0.5761) H3A(0.5272)
 H3B(0.5647) H3C(0.5946) H4(0.6536) H5A(0.8337) H5B(0.7852) H5C(0.769)
 H6A(0.6693) H6B(0.712) H6C(0.7707) H7(0.7741) H8A(0.8136) H8B(0.8986)
 H8C(0.8612) H9A(0.8718) H9B(0.8967) H9C(0.8156) H10A(0.5359) H10B(0.532)
 H11A(0.4067) H11B(0.4629) H12(0.4757) H13A(0.5727) H13B(0.4852) H13C(0.5676)
 H14A(0.4734) H14B(0.395) H14C(0.4328) H15(0.7165) H16A(0.681) H16B(0.7567)
 H16C(0.7582) H17A(0.5998) H17B(0.6699) H17C(0.5845) H18(0.6909) H19A(0.5735)
 H19B(0.6597) H19C(0.5997) H20A(0.7325) H20B(0.7841) H20C(0.784) H21A(0.4677)
 H21B(0.5134) H22A(0.3783) H22B(0.4003) H23(0.5986) H24A(0.6811) H24B(0.6818)
 H24C(0.7279) H25A(0.4671) H25B(0.5291) H25C(0.5154) H26(0.437) H27A(0.5365)
 H27B(0.4347) H27C(0.4936) H28A(0.485) H28B(0.4448) H28C(0.5463) H29(0.7277)
 H30A(0.6698) H30B(0.7522) H30C(0.659) H31A(0.6797) H31B(0.7756) H31C(0.7158)
 H32A(0.4292) H32B(0.4577) H33A(0.3569) H33B(0.4227)
 Fixed Z: H1(0.321) H2A(0.3821) H2B(0.407) H2C(0.3626) H3A(0.2795) H3B(0.3286)
 H3C(0.2537) H4(0.1629) H5A(0.1824) H5B(0.1367) H5C(0.2141) H6A(0.0977)
 H6B(0.0657) H6C(0.1004) H7(0.2913) H8A(0.3556) H8B(0.326) H8C(0.2952)
 H9A(0.1872) H9B(0.2277) H9C(0.18) H10A(0.1828) H10B(0.1474) H11A(0.2104)
 H11B(0.2748) H12(0.4747) H13A(0.5454) H13B(0.5416) H13C(0.5027) H14A(0.4039)
 H14B(0.4415) H14C(0.3766) H15(0.3458) H16A(0.4467) H16B(0.3946) H16C(0.4462)
 H17A(0.2866) H17B(0.2976) H17C(0.3406) H18(0.5033) H19A(0.5293) H19B(0.536)
 H19C(0.4733) H20A(0.4027) H20B(0.4699) H20C(0.4176) H21A(0.4058) H21B(0.3673)
 H22A(0.3211) H22B(0.3095) H23(0.0549) H24A(0.1781) H24B(0.1424) H24C(0.109)
 H25A(0.1108) H25B(0.1356) H25C(0.1795) H26(0.0541) H27A(-0.0238) H27B(-0.0163)
 H27C(0.0439) H28A(-0.0128) H28B(-0.0577) H28C(-0.0519) H29(0.1011)
 H30A(0.1104) H30B(0.0642) H30C(0.0325) H31A(-0.0336) H31B(-0.0065)
 H31C(0.0011) H32A(0.1554) H32B(0.2307) H33A(0.2043) H33B(0.1512)
;