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_4129655
_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, C26 H24 N2 Ti, C7 H8'
_chemical_formula_sum            'C39 H47 Cl3 N3 Ti Zn'
_chemical_formula_weight         777.41
_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             2014-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                105.894(2)
_cell_angle_beta                 102.502(2)
_cell_angle_gamma                104.711(2)
_cell_formula_units_Z            2
_cell_length_a                   11.1136(5)
_cell_length_b                   13.0349(6)
_cell_length_c                   15.1054(7)
_cell_measurement_reflns_used    9870
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.477
_cell_measurement_theta_min      2.62
_cell_volume                     1936.99(16)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_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 0.997
_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  0.0298
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            51179
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.601
_diffrn_reflns_theta_min         1.473
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.063
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6789
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0635 before and 0.0445 after correction.
The Ratio of minimum to maximum transmission is 0.9105.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             810
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     557
_refine_ls_number_reflns         8972
_refine_ls_number_restraints     567
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0307P)^2^+1.1034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7681
_reflns_number_total             8972
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b09223_si_002.cif
_cod_data_source_block           p-1_a
_cod_original_cell_volume        1936.98(16)
_cod_database_code               4129655
_shelx_estimated_absorpt_t_max   0.865
_shelx_estimated_absorpt_t_min   0.816
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1_1-C2_1
 C1_2-C2_2
 C1_3-C2_3
 1.509 with sigma of 0.011
 C2_1-C3_1
 C2_2-C3_2
 C2_3-C3_3
 1.385 with sigma of 0.012
 C2_1-C7_1
 C2_2-C7_2
 C2_3-C7_3
 1.385 with sigma of 0.012
 C3_1-C4_1
 C3_2-C4_2
 C3_3-C4_3
 1.384 with sigma of 0.01
 C4_1-C5_1
 C4_2-C5_2
 C4_3-C5_3
 1.379 with sigma of 0.015
 C5_1-C6_1
 C5_2-C6_2
 C5_3-C6_3
 1.379 with sigma of 0.015
 C6_1-C7_1
 C6_2-C7_2
 C6_3-C7_3
 1.384 with sigma of 0.01
 C1_1-C3_1
 C1_2-C3_2
 C1_3-C3_3
 2.52 with sigma of 0.017
 C1_1-C7_1
 C1_2-C7_2
 C1_3-C7_3
 2.52 with sigma of 0.017
 C3_1-C7_1
 C3_2-C7_2
 C3_3-C7_3
 2.374 with sigma of 0.018
 C2_1-C4_1
 C2_2-C4_2
 C2_3-C4_3
 2.41 with sigma of 0.019
 C3_1-C5_1
 C3_2-C5_2
 C3_3-C5_3
 2.396 with sigma of 0.019
 C4_1-C6_1
 C4_2-C6_2
 C4_3-C6_3
 2.386 with sigma of 0.022
 C5_1-C7_1
 C5_2-C7_2
 C5_3-C7_3
 2.396 with sigma of 0.019
 C2_1-C6_1
 C2_2-C6_2
 C2_3-C6_3
 2.41 with sigma of 0.019
3. Restrained planarity
 C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2
 C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3
 with sigma of 0.1
4. Rigid bond restraints
 C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2
 C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim C7_1 \\sim
C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim C5_2 \\sim C6_2 \\sim C7_2 \\sim
C1_3 \\sim C2_3 \\sim C3_3 \\sim C4_3 \\sim C5_3 \\sim C6_3 \\sim C7_3: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1_2) \\sim Ueq, Uanis(C2_2) \\sim Ueq, Uanis(C3_2) \\sim Ueq,
Uanis(C4_2) \\sim Ueq, Uanis(C5_2) \\sim Ueq, Uanis(C6_2) \\sim Ueq,
Uanis(C7_2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1_3) \\sim Ueq, Uanis(C2_3) \\sim Ueq, Uanis(C3_3) \\sim Ueq,
Uanis(C4_3) \\sim Ueq, Uanis(C5_3) \\sim Ueq, Uanis(C6_3) \\sim Ueq,
Uanis(C7_3) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
6. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2
 C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=0.5*(1-FVAR(2))
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=0.5*FVAR(2)
 Fixed Sof: C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C2(0.5) C3(0.5) H3(0.5) C4(0.5)
 H4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5) C7(0.5) H7(0.5)
8.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10)
8.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C20(H20A,H20B), C27(H27A,H27B), C29(H29A,H29B), C31(H31A,H31B)
8.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C3(H3),
 C4(H4), C5(H5), C6(H6), C7(H7), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7)
8.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C1(H1A,H1B,
 H1C), C1(H1A,H1B,H1C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              54151
_shelx_hkl_checksum              67030
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id OCmf_547
_olex2_submission_special_instructions 'No special instructions were received'