Mechanistic Investigation of Intramolecular Aminoalkene and Aminoalkyne Hydroamination/Cyclization Catalyzed by Highly Electrophilic, Tetravalent Constrained Geometry 4d and 5f Complexes. Evidence for an M-N σ-Bonded Insertive Pathway
Bryan D. Stubbert; Tobin J. Marks; Journal of the American Chemical Society 129 (2007) 6149–6167; doi:10.1021/ja0675898

data_4109413
_publ_contact_author_email       t-marks@northwestern.edu
_publ_contact_author_name        'Tobin J. Marks'
_publ_section_title
;
 Mechanistic Investigation of Intramolecular Aminoalkene and Aminoalkyne
 Hydroamination/Cyclization Catalyzed by Highly Electrophilic, Tetravalent
 Constrained Geometry 4d and 5f Complexes. Evidence for an M-N \s-Bonded
 Insertive Pathway
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6149
_journal_page_last               6167
_journal_paper_doi               10.1021/ja0675898
_journal_volume                  129
_journal_year                    2007
_chemical_formula_moiety         'C31 H54 N2 O Si Th'
_chemical_formula_sum            'C31 H54 N2 O Si Th'
_chemical_formula_weight         730.89
_chemical_name_common            (CGC)Th(NMe2)OAr
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 96.41(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.929(6)
_cell_length_b                   10.039(7)
_cell_length_c                   32.12(2)
_cell_measurement_temperature    153(2)
_cell_volume                     3182(4)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      153(2)
_diffrn_measured_fraction_theta_full 0.99
_diffrn_measured_fraction_theta_max 0.919
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1252
_diffrn_reflns_av_sigmaI/netI    0.1212
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            28708
_diffrn_reflns_theta_full        26
_diffrn_reflns_theta_max         28.87
_diffrn_reflns_theta_min         1.28
_exptl_absorpt_coefficient_mu    4.749
_exptl_absorpt_correction_T_max  0.79
_exptl_absorpt_correction_T_min  0.73
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       plate
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.061
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.050
_refine_diff_density_max         2.838
_refine_diff_density_min         -1.673
_refine_diff_density_rms         0.217
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.937
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     342
_refine_ls_number_reflns         7692
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.937
_refine_ls_R_factor_all          0.0954
_refine_ls_R_factor_gt           0.0476
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0321P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0875
_refine_ls_wR_factor_ref         0.1007
_reflns_number_gt                4866
_reflns_number_total             7692
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0675898si20061024_063202.cif
_cod_data_source_block           s89sm_face
_cod_database_code               4109413