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_4109412
_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         'C17 H33 Cl N2 Si Zr'
_chemical_formula_sum            'C17 H33 Cl N2 Si Zr'
_chemical_formula_weight         420.21
_chemical_name_common            (CGC)Zr(NMe2)(Cl)
_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                82.11(3)
_cell_angle_beta                 74.85(3)
_cell_angle_gamma                63.74(4)
_cell_formula_units_Z            2
_cell_length_a                   8.465(4)
_cell_length_b                   8.780(2)
_cell_length_c                   15.839(6)
_cell_measurement_temperature    153(2)
_cell_volume                     1018.7(8)
_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 0.897
_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  0.0506
_diffrn_reflns_av_sigmaI/netI    0.0509
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            9247
_diffrn_reflns_theta_full        26.0
_diffrn_reflns_theta_max         28.56
_diffrn_reflns_theta_min         1.33
_exptl_absorpt_coefficient_mu    0.729
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.86
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       columnar
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.052
_refine_diff_density_max         1.793
_refine_diff_density_min         -0.639
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         4668
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0663P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1067
_refine_ls_wR_factor_ref         0.1107
_reflns_number_gt                3968
_reflns_number_total             4668
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0675898si20061024_063139.cif
_cod_data_source_block           s85rm_face
_cod_original_cell_volume        1018.6(8)
_cod_database_code               4109412