Reversible oxidative-addition and reductive-elimination of thiophene from a titanium complex and its thermally-induced hydrodesulphurization chemistry.
Gómez-Torres, Alejandra; Aguilar-Calderón, J Rolando; Saucedo, Carlos; Jordan, Aldo; Metta-Magaña, Alejandro; Pinter, Balazs; Fortier, Skye; Chemical communications (Cambridge, England) 56 (2020) 1545–1548; doi:10.1039/c9cc09267f

data_7125695
_publ_section_title
;
 Reversible oxidative-addition and reductive-elimination of thiophene from
 a titanium complex and its thermally-induced hydrodesulphurization
 chemistry.
;
_journal_issue                   10
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1545
_journal_page_last               1548
_journal_paper_doi               10.1039/c9cc09267f
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C65 H92 N6 S Ti, 3(C3)'
_chemical_formula_sum            'C74 H92 N6 S Ti'
_chemical_formula_weight         1145.49
_chemical_name_systematic        DippL2Ti_k2-S(CH)3CH
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Light-sensitive,Photo-sensitive
_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   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc23wzmm
_audit_creation_date             2019-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-03 deposited with the CCDC.	2019-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.80(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.184(4)
_cell_length_b                   16.616(3)
_cell_length_c                   23.789(5)
_cell_measurement_reflns_used    9842
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.926
_cell_measurement_theta_min      2.361
_cell_volume                     7089(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0652
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            135214
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.366
_diffrn_reflns_theta_min         2.090
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.193
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1194 before and 0.0627 after correction. The Ratio of minimum to maximum transmission is 0.9171. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.073
_exptl_crystal_description       needle
_exptl_crystal_F_000             2464
_exptl_crystal_recrystallization_method 'Toluene/hexanes at -32 celsius'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.313
_refine_diff_density_min         -0.642
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     765
_refine_ls_number_reflns         14454
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0921
_refine_ls_R_factor_gt           0.0673
_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^)+(0.1038P)^2^+8.6153P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1837
_refine_ls_wR_factor_ref         0.2059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10775
_reflns_number_total             14454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc09267f2.cif
_cod_data_source_block           at_bthio_2_0m
_cod_depositor_comments          'Adding full bibliography for 7125695.cif.'
_cod_database_code               7125695
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.972
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C20(H20), C11(H11), C8(H8), C23(H23), C59(H59), C56(H56), C44(H44), C47(H47)
2.b Aromatic/amide H refined with riding coordinates:
 C37(H37), C64(H64), C36(H36), C40(H40), C6(H6), C4(H4), C54(H54), C5(H5),
 C18(H18), C62(H62), C52(H52), C41(H41), C53(H53), C16(H16), C63(H63), C42(H42),
  C17(H17)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C32(H32A,H32B,
 H32C), C9(H9A,H9B,H9C), C21(H21A,H21B,H21C), C10(H10A,H10B,H10C), C12(H12A,
 H12B,H12C), C30(H30A,H30B,H30C), C22(H22A,H22B,H22C), C61(H61A,H61B,H61C),
 C34(H34A,H34B,H34C), C33(H33A,H33B,H33C), C24(H24A,H24B,H24C), C58(H58A,H58B,
 H58C), C25(H25A,H25B,H25C), C57(H57A,H57B,H57C), C60(H60A,H60B,H60C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C49(H49A,H49B,H49C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              85854
_olex2_submission_special_instructions 'No special instructions were received'