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_1564734
_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(C16H23N)
_chemical_formula_sum            'C46 H61 N Ti'
_chemical_formula_weight         675.85
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2017/1
_audit_update_record
;
2021-03-15 deposited with the CCDC.	2021-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0155(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6868(8)
_cell_length_b                   11.3121(6)
_cell_length_c                   22.0238(12)
_cell_measurement_reflns_used    9339
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.87
_cell_measurement_theta_min      2.44
_cell_volume                     3658.4(3)
_computing_cell_refinement       'Bruker SAINT V8.37A'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT V8.37A'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_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 APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            193658
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.971
_diffrn_reflns_theta_min         1.653
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.268
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9239
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       block
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.200
_refine_diff_density_max         0.958
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     450
_refine_ls_number_reflns         16067
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0600P)^2^+0.9000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0998
_refine_ls_wR_factor_ref         0.1082
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13309
_reflns_number_total             16067
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04334j2.cif
_cod_data_source_block           2a
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               1564734
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_min   0.901
_shelx_estimated_absorpt_t_max   0.948
_shelx_res_checksum              890
_shelx_hkl_checksum              10021