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_1515380
_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 H74 N4 Si3 U'
_chemical_formula_sum            'C33 H74 N4 Si3 U'
_chemical_formula_weight         849.26
_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                 92.508(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.347(2)
_cell_length_b                   22.333(6)
_cell_length_c                   18.920(5)
_cell_measurement_reflns_used    6641
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.39
_cell_measurement_theta_min      2.15
_cell_volume                     3945.7(17)
_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(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.999
_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_unetI/netI     0.0797
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            6958
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         2.118
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.231
_exptl_absorpt_correction_T_max  0.4305
_exptl_absorpt_correction_T_min  0.2905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2007/2 (Bruker,2007) was used for absorption correction.
wR2(int) was 0.1113 before and 0.0781 after correction.
The Ratio of minimum to maximum transmission is 0.6748.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            ORANGE
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       ROD
_exptl_crystal_F_000             1736
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.293
_refine_diff_density_min         -6.101
_refine_diff_density_rms         0.237
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.372
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     384
_refine_ls_number_reflns         6958
_refine_ls_number_restraints     309
_refine_ls_restrained_S_all      1.352
_refine_ls_R_factor_all          0.1240
_refine_ls_R_factor_gt           0.1110
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+116.4027P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2144
_refine_ls_wR_factor_ref         0.2195
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6180
_reflns_number_total             6958
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc00182f2.cif
_cod_data_source_block           3a
_cod_depositor_comments
'Adding full bibliography for 1515379--1515382.cif.'
_cod_original_cell_volume        3945.8(17)
_cod_database_code               1515380
_shelxl_version_number           2013-4
_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. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C7(H7), C12(H12), C15(H15), C18(H18), C23(H23), C26(H26),
 C29(H29)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C10(H10A,H10B), C11(H11A,H11B), C21(H21A,H21B), C22(H22A,H22B),
 C32(H32A,H32B), C33(H33A,H33B)
3.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C)
;