Reversible C-C bond formation in group 4 metal complexes: nitrile extrusion <i>via</i> β-aryl elimination.
Kulyabin, Pavel S.; Goryunov, Georgy P.; Iashin, Andrei N.; Mladentsev, Dmitry Y.; Uborsky, Dmitry V.; Ehm, Christian; Canich, Jo Ann M.; Hagadorn, John R.; Voskoboynikov, Alexander Z.; Chemical science 15 (2024) 15825–15834; doi:10.1039/d4sc02173h

data_1572545
_publ_section_title
;
 Reversible C-C bond formation in group 4 metal complexes: nitrile
 extrusion <i>via</i> &#x3b2;-aryl elimination.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              15825
_journal_page_last               15834
_journal_paper_doi               10.1039/d4sc02173h
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C27 H36 Hf N2 Si'
_chemical_formula_sum            'C27 H36 Hf N2 Si'
_chemical_formula_weight         595.16
_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             2017-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2023-10-16 deposited with the CCDC.	2024-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                88.4150(10)
_cell_angle_beta                 72.4220(10)
_cell_angle_gamma                63.5670(10)
_cell_formula_units_Z            2
_cell_length_a                   9.6477(7)
_cell_length_b                   10.3442(8)
_cell_length_c                   15.3145(12)
_cell_measurement_reflns_used    8821
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.772
_cell_measurement_theta_min      2.433
_cell_volume                     1294.42(17)
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            APEX-II
_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 APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12591
_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         26.022
_diffrn_reflns_theta_min         1.406
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.092
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.4605
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1186 before and 0.0478 after correction. The Ratio of minimum to maximum transmission is 0.6291. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       prism
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.992
_refine_diff_density_min         -2.551
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         5091
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0338
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0613P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0881
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4704
_reflns_number_total             5091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02173h7.cif
_cod_data_source_block           1977
_cod_depositor_comments
'Adding full bibliography for 1572545--1572551.cif.'
_cod_database_code               1572545
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.579
_shelx_estimated_absorpt_t_min   0.495
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H1E)=Sof(H1C)=Sof(H1D)=1-FVAR(1)
 Sof(H1B)=Sof(H1A)=Sof(H1F)=FVAR(1)
 Sof(H2A)=Sof(H2C)=Sof(H2D)=1-FVAR(2)
 Sof(H2E)=Sof(H2F)=Sof(H2B)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C18(H18), C19(H19), C20(H20), C23(H23), C24(H24),
 C25(H25), C26(H26)
3.c Disordered Me refined with riding coordinates:
 C1(H1B,H1A,H1F,H1E,H1C,H1D), C2(H2E,H2F,H2B,H2A,H2C,H2D)
3.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              98840
_olex2_submission_special_instructions 'No special instructions were received'