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_1515382
_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         'C40 H82 N4 Si3 Th'
_chemical_formula_sum            'C40 H82 N4 Si3 Th'
_chemical_formula_weight         935.40
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4715)
;
_cell_angle_alpha                60.713(3)
_cell_angle_beta                 89.936(3)
_cell_angle_gamma                69.909(3)
_cell_formula_units_Z            8
_cell_length_a                   18.7387(6)
_cell_length_b                   24.4559(7)
_cell_length_c                   24.9335(8)
_cell_measurement_reflns_used    27466
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.42
_cell_measurement_theta_min      3.5820
_cell_volume                     9163.0(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova Cu'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0154619000
_diffrn_orient_matrix_UB_12      0.0748202000
_diffrn_orient_matrix_UB_13      -0.0489496000
_diffrn_orient_matrix_UB_21      0.0099626000
_diffrn_orient_matrix_UB_22      0.0133423000
_diffrn_orient_matrix_UB_23      0.0532896000
_diffrn_orient_matrix_UB_31      0.0875038000
_diffrn_orient_matrix_UB_32      -0.0198625000
_diffrn_orient_matrix_UB_33      0.0003511000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0536
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            81199
_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         74.910
_diffrn_reflns_theta_min         3.547
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    11.459
_exptl_absorpt_correction_T_max  0.874
_exptl_absorpt_correction_T_min  0.381
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3856
_exptl_crystal_size_max          0.1262
_exptl_crystal_size_mid          0.0669
_exptl_crystal_size_min          0.0117
_refine_diff_density_max         2.881
_refine_diff_density_min         -2.534
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1860
_refine_ls_number_reflns         36576
_refine_ls_number_restraints     1920
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0678
_refine_ls_R_factor_gt           0.0548
_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^)+(0.0517P)^2^+43.3969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1324
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.000
_reflns_number_gt                30222
_reflns_number_total             36576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc00182f2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1515379--1515382.cif.'
_cod_database_code               1515382
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C40 H82 N4 Si3 Th'
_chemical_oxdiff_usercomment
'THBGLQ #12060 FOR BMG/STL ON MICROMOUNT IN FOMBLIN OIL'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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. Restrained distances
 C148-Th4
 -3.6 with sigma of 0.02
 C146-Th4
 -3.6 with sigma of 0.02
 C151-C154
 -0.3 with sigma of 0.01
 Si12-C143 \\sim Si12-C146 \\sim Si12-C152 \\sim Si12-C149
 with sigma of 0.02
 C149-C143 \\sim C152-C146
 with sigma of 0.02
 C155-C143 \\sim C155-C146 \\sim C155-C152 \\sim C155-C149
 with sigma of 0.02
 C150-C149 \\sim C152-C153 \\sim C154-C152 \\sim C146-C147 \\sim C144-C143
\\sim C145-C143 \\sim C148-
 C146 \\sim C151-C149
 with sigma of 0.02
 C147-C148 \\sim C145-C144 \\sim C153-C154 \\sim C151-C150
 with sigma of 0.02
 C150-C144 \\sim C151-C145 \\sim C153-C147 \\sim C154-C148
 with sigma of 0.02
 Si12-C150 \\sim Si12-C151 \\sim Si12-C153 \\sim Si12-C154 \\sim Si12-C147
\\sim Si12-C148 \\sim Si12-
 C144 \\sim Si12-C145
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C143 \\sim C144 \\sim C145 \\sim C151 \\sim C154 \\sim C146 \\sim C147 \\sim
C148 \\sim C149 \\sim C150 \\sim C152 \\sim C153 \\sim Si12: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. 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
5. Others
 Sof(C146)=Sof(H146)=Sof(C147)=Sof(H14N)=Sof(H14O)=Sof(H14P)=Sof(C148)=
 Sof(H14Q)=Sof(H14R)=Sof(H14S)=Sof(C152)=Sof(H152)=Sof(C153)=Sof(H15G)=
 Sof(H15H)=Sof(H15I)=Sof(C154)=Sof(H15J)=Sof(H15K)=Sof(H15L)=1-FVAR(1)
 Sof(C143)=Sof(H143)=Sof(C144)=Sof(H14H)=Sof(H14I)=Sof(H14J)=Sof(C145)=
 Sof(H14K)=Sof(H14L)=Sof(H14M)=Sof(C149)=Sof(H149)=Sof(C150)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C151)=Sof(H15D)=Sof(H15E)=Sof(H15F)=FVAR(1)
6.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), C41(H41), C44(H44), C47(H47), C52(H52), C55(H55), C58(H58), C63(H63),
  C66(H66), C69(H69), C81(H81), C84(H84), C87(H87), C92(H92), C95(H95),
 C98(H98), C103(H103), C106(H106), C109(H109), C121(H121), C124(H124),
 C127(H127), C132(H132), C135(H135), C138(H138), C143(H143), C146(H146),
 C149(H149), C152(H152), C155(H155)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C21(H21A,H21B), C22(H22A,H22B), C32(H32A,
 H32B), C33(H33A,H33B), C34(H34A,H34B), C50(H50A,H50B), C51(H51A,H51B),
 C61(H61A,H61B), C62(H62A,H62B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
  C90(H90A,H90B), C91(H91A,H91B), C101(H10F,H10G), C102(H10H,H10I), C112(H11I,
 H11J), C113(H11K,H11L), C114(H11M,H11N), C130(H13A,H13B), C131(H13C,H13D),
 C141(H14D,H14E), C142(H14F,H14G), C158(H15S,H15T), C159(H15U,H15V), C160(H16A,
 H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C76(H76), C77(H77),
 C78(H78), C79(H79), C80(H80), C116(H116), C117(H117), C118(H118), C119(H119),
 C120(H120), C162(H162), C163(H163), C164(H164), C165(H165), C166(H166)
6.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C13(H13T,H13U,H13V), C14(H14T,H14U,H14V), C16(H16C,
 H16D,H16E), 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), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C),
 C49(H49A,H49B,H49C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C),
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C),
 C97(H97A,H97B,H97C), C99(H99A,H99B,H99C), C100(H10C,H10D,H10E), C104(H10J,H10K,
 H10L), C105(H10M,H10N,H10O), C107(H10P,H10Q,H10R), C108(H10S,H10T,H10U),
 C110(H11C,H11D,H11E), C111(H11F,H11G,H11H), C122(H12A,H12B,H12C), C123(H12D,
 H12E,H12F), C125(H12G,H12H,H12I), C126(H12J,H12K,H12L), C128(H12M,H12N,H12O),
 C129(H12P,H12Q,H12R), C133(H13E,H13F,H13G), C134(H13H,H13I,H13J), C136(H13K,
 H13L,H13M), C137(H13N,H13O,H13P), C139(H13Q,H13R,H13S), C140(H14A,H14B,H14C),
 C144(H14H,H14I,H14J), C145(H14K,H14L,H14M), C147(H14N,H14O,H14P), C148(H14Q,
 H14R,H14S), C150(H15A,H15B,H15C), C151(H15D,H15E,H15F), C153(H15G,H15H,H15I),
 C154(H15J,H15K,H15L), C156(H15M,H15N,H15O), C157(H15P,H15Q,H15R)
;