Selective Propargylic C(sp 3 )‒H Activation of Methyl-Substituted Alkynes Versus [2+2] Cycloaddition at a Titanium Imido Template
Fischer, Malte; Manssen, Manfred; Schmidtmann, Marc M.S.; Klüner, Thorsten T.K.; Beckhaus, Ruediger; Chemical Science  (2021) –; doi:10.1039/D1SC04334J

data_1564733
_publ_section_title
;
 &#x000D; Selective Propargylic C(sp&#x000D; &#x000D; 3&#x000D; &#x000D;
 )--H Activation of Methyl-Substituted Alkynes Versus [2+2] Cycloaddition
 at a Titanium Imido Template&#x000D;
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04334J
_journal_year                    2021
_chemical_formula_structural     Ti(C15H19)2(C21H25N)
_chemical_formula_sum            'C51 H63 N Ti'
_chemical_formula_weight         737.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_audit_update_record
;
2021-03-15 deposited with the CCDC.	2021-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.314(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.3982(6)
_cell_length_b                   19.9869(7)
_cell_length_c                   10.3954(4)
_cell_measurement_reflns_used    6700
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      57.68
_cell_measurement_theta_min      2.35
_cell_volume                     3905.3(2)
_computing_cell_refinement       'Bruker SAINT V8.40A'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT V8.40A'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Photon III CPAD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1157
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            71245
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        58.926
_diffrn_reflns_theta_max         58.925
_diffrn_reflns_theta_min         2.351
_diffrn_source                   'I\mS microfocus'
_exptl_absorpt_coefficient_mu    2.120
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       needle
_exptl_crystal_F_000             1592
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         5606
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0642
_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
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+3.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4334
_reflns_number_total             5606
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04334j2.cif
_cod_data_source_block           I
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1564733
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.849
_shelx_estimated_absorpt_t_max   0.979
_shelx_res_checksum              33734
_shelx_hkl_checksum              41399