Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia Surrogate: Synthesis of N-Silylenamines as Reactive Synthons.
Lui, Erica K. J.; Brandt, Jason W.; Schafer, Laurel L.; Journal of the American Chemical Society 140 (2018) 4973–4976; doi:10.1021/jacs.7b13783

data_4132001
_publ_section_title
;
 Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia
 Surrogate: Synthesis of N-Silylenamines as Reactive Synthons.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4973
_journal_page_last               4976
_journal_paper_doi               10.1021/jacs.7b13783
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         '4(C61 H64 N4 O2 Si Ti)'
_chemical_formula_sum            'C244 H256 N16 O8 Si4 Ti4'
_chemical_formula_weight         3844.59
_chemical_name_systematic
'N-triphenylsilylimidobis(N-2,6-diisopropylphenylbenzamido)pyridine titanium(IV)'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-09-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                72.79
_cell_angle_beta                 77.72
_cell_angle_gamma                72.76
_cell_formula_units_Z            1
_cell_length_a                   12.843
_cell_length_b                   20.558
_cell_length_c                   23.390
_cell_measurement_reflns_used    9789
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.006
_cell_measurement_theta_min      2.373
_cell_volume                     5580.907
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'APEX2 DUO'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            124636
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.063
_diffrn_reflns_theta_min         1.225
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  0.9635
_exptl_absorpt_correction_T_min  0.9099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0440 before and 0.0405 after correction.
The Ratio of minimum to maximum transmission is 0.9444.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.144
_exptl_crystal_description       prism
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.401
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1278
_refine_ls_number_reflns         32571
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0484P)^2^+1.8338P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25603
_reflns_number_total             32571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b13783_si_004.cif
_cod_data_source_block           ls590_0m
_cod_original_cell_volume        5580.9
_cod_database_code               4132001
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.914
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C43B) = Uanis(C1)
Uanis(C44B) = Uanis(C2)
Uanis(C45B) = Uanis(C3)
Uanis(C46B) = Uanis(C4)
Uanis(C47B) = Uanis(C5)
Uanis(C48B) = Uanis(C6)
3. Others
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(H6)=1-FVAR(1)
 Sof(C43B)=Sof(C44B)=Sof(H44B)=Sof(C47B)=Sof(H47B)=Sof(C48B)=Sof(H48B)=
 Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46B)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C58B(H58B), C36B(H36B), C39B(H39B), C55B(H55B), C59A(H59D), C40A(H40D),
 C56A(H56D), C37A(H37D)
4.b Aromatic/amide H refined with riding coordinates:
 C25B(H25B), C22B(H22B), C18B(H18B), C53B(H53B), C51B(H51B), C29B(H29B),
 C27B(H27B), C52B(H52B), C21B(H21B), C26B(H26B), C33B(H33B), C34B(H34B),
 C28B(H28B), C32B(H32B), C13B(H13B), C2B(H2B), C14B(H14B), C19B(H19B), C6B(H6B),
  C1EA(H1EA), C17B(H17B), C8B(H8B), C4B(H4B), C11B(H11B), C5B(H5B), C16B(H16B),
 C20B(H20B), C15B(H15B), C3B(H3B), C9B(H9B), C10B(H10B), C19A(H19A), C49A(H49A),
  C54A(H54A), C2A(H2A), C6A(H6A), C45A(H45A), C46A(H46A), C48A(H48A),
 C18A(H18A), C8A(H8A), C53A(H53A), C52A(H52A), C14A(H14A), C12A(H12A),
 C20A(H20A), C5A(H5A), C16A(H16A), C23A(H23A), C17A(H17A), C4A(H4A), C35A(H35A),
  C30A(H30A), C47A(H47A), C11A(H11A), C3A(H3A), C26A(H26A), C33A(H33A),
 C15A(H15A), C10A(H10A), C21A(H21A), C9A(H9A), C34A(H34A), C22A(H22A),
 C27A(H27A), C28A(H28A), C29A(H29A), C44B(H44B), C47B(H47B), C48B(H48B),
 C45B(H45B), C46B(H46B), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
4.c Idealised Me refined as rotating group:
 C57B(H57A,H57B,H57C), C59B(H59A,H59B,H59C), C40B(H40A,H40B,H40C), C38B(H38A,
 H38B,H38C), C41B(H41A,H41B,H41C), C56B(H56A,H56B,H56C), C60B(H60A,H60B,H60C),
 C37B(H37A,H37B,H37C), C61A(H61A,H61B,H61C), C60A(H60D,H60E,H60F), C41A(H41D,
 H41E,H41F), C57A(H57D,H57E,H57F), C58A(H58A,H58C,H58D), C42A(H42A,H42B,H42C),
 C39A(H39A,H39C,H39D), C38A(H38D,H38E,H38F)
;
_shelx_res_checksum              67562
_shelx_hkl_checksum              25548
_shelx_fab_checksum              89615
_olex2_submission_original_sample_id ls590
_olex2_submission_special_instructions 'No special instructions were received'