Mechanism of the Ti(III)-Catalyzed Acyloin-Type Umpolung: A Catalyst-Controlled Radical Reaction.
Streuff, Jan; Feurer, Markus; Frey, Georg; Steffani, Alberto; Kacprzak, Sylwia; Weweler, Jens; Leijendekker, Leonardus H.; Kratzert, Daniel; Plattner, Dietmar A.; Journal of the American Chemical Society 137 (2015) 14396–14405; doi:10.1021/jacs.5b09223

data_4129656
_publ_section_title
;
 Mechanism of the Ti(III)-Catalyzed Acyloin-Type Umpolung: A
 Catalyst-Controlled Radical Reaction.
;
_journal_issue                   45
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14396
_journal_page_last               14405
_journal_paper_doi               10.1021/jacs.5b09223
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C6 H15 Cl3 N Zn, C6 H16 N'
_chemical_formula_sum            'C12 H31 Cl3 N2 Zn'
_chemical_formula_weight         375.11
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.071(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5110(8)
_cell_length_b                   10.9853(7)
_cell_length_c                   13.2890(9)
_cell_measurement_reflns_used    9219
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.487
_cell_measurement_theta_min      2.407
_cell_volume                     1823.8(2)
_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, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0248
_diffrn_reflns_av_unetI/netI     0.0111
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            48773
_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         27.496
_diffrn_reflns_theta_min         1.630
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.774
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5766
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0890 before and 0.0389 after correction.
The Ratio of minimum to maximum transmission is 0.7733.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.512
_exptl_crystal_size_mid          0.301
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         4191
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0176
_refine_ls_R_factor_gt           0.0161
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0215P)^2^+0.7086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0408
_refine_ls_wR_factor_ref         0.0414
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3962
_reflns_number_total             4191
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b09223_si_003.cif
_cod_data_source_block           p21c_a
_cod_database_code               4129656
_shelx_estimated_absorpt_t_max   0.707
_shelx_estimated_absorpt_t_min   0.464
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,H11B)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              68966
_shelx_hkl_checksum              40879
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id OC_DK_JS525
_olex2_submission_special_instructions 'No special instructions were received'