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_1572550
_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         'C35 H50 Hf N4 Si'
_chemical_formula_sum            'C35 H50 Hf N4 Si'
_chemical_formula_weight         733.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-10-16 deposited with the CCDC.	2024-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.1939(14)
_cell_length_b                   15.9751(10)
_cell_length_c                   27.1492(16)
_cell_measurement_reflns_used    4274
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      25.29
_cell_measurement_theta_min      2.52
_cell_volume                     7023.5(9)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III detector'
_diffrn_measurement_method       'phi and omega shutterless scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1257
_diffrn_reflns_av_unetI/netI     0.0707
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            67522
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.999
_diffrn_reflns_theta_min         1.941
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    3.032
_exptl_absorpt_correction_T_max  0.8622
_exptl_absorpt_correction_T_min  0.7189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1249 before and 0.0846 after correction.
The Ratio of minimum to maximum transmission is 0.8338.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.122
_refine_diff_density_max         1.902
_refine_diff_density_min         -1.151
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         9319
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0234P)^2^+5.7337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0846
_refine_ls_wR_factor_ref         0.0978
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6657
_reflns_number_total             9319
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02173h7.cif
_cod_data_source_block           qq
_cod_depositor_comments
'Adding full bibliography for 1572545--1572551.cif.'
_cod_database_code               1572550
_shelx_shelxl_version_number     2018/3
_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:
 C26(H26), C1(H1), C18(H18), C32(H32)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C12(H12), C24(H24), C13(H13), C22(H22), C9(H9), C7(H7), C23(H23),
 C8(H8), C6(H6)
2.c Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C31(H31A,H31B,H31C), C28(H28A,H28B,H28C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C3(H3A,H3B,H3C), C20(H20A,H20B,H20C), C2(H2A,H2B,
 H2C), C27(H27A,H27B,H27C), C19(H19A,H19B,H19C), C34(H34A,H34B,H34C), C33(H33A,
 H33B,H33C)
;
_shelx_res_checksum              60969
_olex2_submission_special_instructions 'No special instructions were received'