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_4109410
_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         'C42 H90 Cl2 N4 Si6 Th2'
_chemical_formula_sum            'C42 H90 Cl2 N4 Si6 Th2'
_chemical_formula_weight         1354.70
_chemical_name_common            '[(CGC)Th[N(SiMe3)2]Cl]2'
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_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_method           SHELXL-97
_cell_angle_alpha                74.700(13)
_cell_angle_beta                 83.260(10)
_cell_angle_gamma                63.205(16)
_cell_formula_units_Z            1
_cell_length_a                   10.896(3)
_cell_length_b                   11.550(2)
_cell_length_c                   13.120(2)
_cell_measurement_temperature    153(2)
_cell_volume                     1421.6(6)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      153(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.920
_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  0.0260
_diffrn_reflns_av_sigmaI/netI    0.0194
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            3208
_diffrn_reflns_theta_full        26.3
_diffrn_reflns_theta_max         28.0
_diffrn_reflns_theta_min         1.61
_exptl_absorpt_coefficient_mu    5.475
_exptl_absorpt_correction_T_max  0.50
_exptl_absorpt_correction_T_min  0.25
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_process_details   '(North et al., 1968)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.582
_exptl_crystal_description       block
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.918
_refine_diff_density_min         -0.730
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         2337
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0206
_refine_ls_R_factor_gt           0.0200
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0378P)^2^+1.7830P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0532
_refine_ls_wR_factor_ref         0.0535
_reflns_number_gt                2294
_reflns_number_total             2337
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0675898si20061024_063056.cif
_cod_data_source_block           s83rm_psiell
_cod_database_code               4109410