A titanium redox-switch enables reversible C-C bond forming and splitting reactions.
G Jafari, Mehrafshan; Fehn, Dominik; Sandoval-Pauker, Christian; Gau, Michael R.; Meyer, Karsten; Pinter, Balazs; Mindiola, Daniel J.; Reinholdt, Anders; Chemical science 16 (2025) 17714–17724; doi:10.1039/d5sc04824a

data_1575522
_publ_section_title
;
 A titanium redox-switch enables reversible C-C bond forming and splitting
 reactions.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              17714
_journal_page_last               17724
_journal_paper_doi               10.1039/d5sc04824a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C70 H110 B2 N16 Ti2, 2(B C24 F20), 4(C4 H10 O)'
_chemical_formula_sum            'C134 H150 B4 F40 N16 O4 Ti2'
_chemical_formula_weight         2947.73
_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     dual
_audit_creation_date             2022-05-06
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2025-04-21 deposited with the CCDC.	2025-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                99.9250(10)
_cell_angle_beta                 92.3010(10)
_cell_angle_gamma                94.2010(10)
_cell_formula_units_Z            1
_cell_length_a                   14.0910(2)
_cell_length_b                   14.8091(2)
_cell_length_c                   16.4769(2)
_cell_measurement_reflns_used    30449
_cell_measurement_temperature    100
_cell_measurement_theta_max      73.9040
_cell_measurement_theta_min      2.7170
_cell_volume                     3372.88(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 2012)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-6000HE
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -62.00  25.00   0.50    2.00    --  -47.04  57.00 -60.00  174
  2  \w    -62.00  25.00   0.50    2.00    --  -47.04  57.00  60.00  174
  3  \w   -120.00 -35.00   0.50    2.00    --  -47.04 -37.00-180.00  170
  4  \w   -118.00 -32.00   0.50    2.00    --  -47.04 -57.00 -60.00  172
  5  \w    -30.00  28.00   0.50    2.00    --  -47.04  19.00-180.00  116
  6  \w    -27.00  24.00   0.50    2.00    --   47.04 -19.00-180.00  102
  7  \w    -27.00  24.00   0.50    2.00    --   47.04 -19.00 150.00  102
  8  \w    -27.00  24.00   0.50    2.00    --   47.04 -19.00-150.00  102
  9  \w    -54.00 -18.00   0.50    6.00    --  -90.00  45.00  60.00   72
 10  \w    -74.00 -17.00   0.50    6.00    --  -90.00  61.00 120.00  114
 11  \w   -114.00 -17.00   0.50    6.00    --  -90.00  80.00 178.26  194
 12  \w   -164.00 -77.00   0.50    6.00    --  -90.00 -30.00 -30.00  174
 13  \w   -164.00 -77.00   0.50    6.00    --  -90.00 -30.00-120.00  174
 14  \w   -114.00 -17.00   0.50    6.00    --  -90.00  80.00-107.85  194
 15  \w    -54.00 -18.00   0.50    6.00    --  -90.00  45.00-180.00   72
 16  \w   -114.00 -17.00   0.50    6.00    --  -90.00  80.00 104.68  194
 17  \w   -164.00 -77.00   0.50    6.00    --  -90.00 -30.00 -90.00  174
 18  \w     92.00 178.00   0.50    6.00    --  104.57  30.00-150.00  172
 19  \w     92.00 178.00   0.50    6.00    --  104.57  30.00-180.00  172
 20  \w     32.00 129.00   0.50    6.00    --  104.57 -80.00  11.58  194
 21  \w     92.00 178.00   0.50    6.00    --  104.57  30.00 120.00  172
 22  \w     32.00 103.00   0.50    6.00    --  104.57 -77.00 -30.00  142
 23  \w     32.00 103.00   0.50    6.00    --  104.57 -77.00-120.00  142
 24  \w     32.00  68.00   0.50    6.00    --  104.57 -61.00 120.00   72
 25  \w     32.00  68.00   0.50    6.00    --  104.57 -61.00   0.00   72
 26  \w     92.00 178.00   0.50    6.00    --  104.57  30.00  90.00  172
 27  \w     32.00 129.00   0.50    6.00    --  104.57 -80.00 110.00  194
 28  \w     32.00  68.00   0.50    6.00    --  104.57 -61.00  30.00   72
 29  \w     32.00  68.00   0.50    6.00    --  104.57 -61.00-150.00   72
 30  \w     32.00 128.00   0.50    6.00    --  104.57 -79.00 -66.83  192
 31  \w     32.00 128.00   0.50    6.00    --  104.57 -79.00-158.25  192
 32  \w   -119.00 -24.00   0.50    2.00    --  -47.04 -77.00  30.00  190
 33  \w     32.00 119.00   0.50    2.00    --   47.04  57.00 150.00  174
 34  \w     24.00 119.00   0.50    2.00    --   47.04  77.00  60.00  190
 35  \w     24.00 119.00   0.50    2.00    --   47.04  77.00 -90.00  190
 36  \w     24.00 119.00   0.50    2.00    --   47.04  77.00 150.00  190
 37  \w     24.00 119.00   0.50    2.00    --   47.04  77.00-150.00  190
 38  \w   -162.00 -90.00   0.50    6.00    --  -90.00 -76.00-136.81  144
 39  \w   -162.00 -77.00   0.50    6.00    --  -90.00 -45.00  30.00  170
 40  \w   -162.00 -67.00   0.50    6.00    --  -90.00 -76.00 -11.83  190
 41  \w   -162.00 -67.00   0.50    6.00    --  -90.00 -77.00  90.00  190
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0059173000
_diffrn_orient_matrix_UB_12      -0.0027754000
_diffrn_orient_matrix_UB_13      -0.0939728000
_diffrn_orient_matrix_UB_21      0.0183495000
_diffrn_orient_matrix_UB_22      0.1055157000
_diffrn_orient_matrix_UB_23      0.0141132000
_diffrn_orient_matrix_UB_31      0.1080766000
_diffrn_orient_matrix_UB_32      -0.0092992000
_diffrn_orient_matrix_UB_33      -0.0023547000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0530
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            72165
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.486
_diffrn_reflns_theta_min         2.726
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.017
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_description       bar
_exptl_crystal_F_000             1522
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.840
_refine_diff_density_min         -0.826
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1013
_refine_ls_number_reflns         13264
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0614
_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^)+(0.1055P)^2^+2.7416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1714
_refine_ls_wR_factor_ref         0.1809
_reflns_number_gt                10927
_reflns_number_total             13264
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04824a2.cif
_cod_data_source_block           9897_cmpd4
_cod_depositor_comments
'Adding full bibliography for 1575521--1575523.cif.'
_cod_database_code               1575522
_shelx_shelxl_version_number     2018/3
_shelx_res_checksum              80056
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.900
_oxdiff_exptl_absorpt_empirical_full_min 0.641