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_1572551
_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         'C41 H46 Hf N4 Si'
_chemical_formula_sum            'C41 H46 Hf N4 Si'
_chemical_formula_weight         801.40
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-02-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_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                120
_cell_formula_units_Z            18
_cell_length_a                   44.5128(8)
_cell_length_b                   44.5128(8)
_cell_length_c                   9.3817(3)
_cell_measurement_reflns_used    6881
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      27.027
_cell_measurement_theta_min      2.414
_cell_volume                     16098.4(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX3 (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0882
_diffrn_reflns_av_unetI/netI     0.0600
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       58
_diffrn_reflns_limit_h_min       -60
_diffrn_reflns_limit_k_max       60
_diffrn_reflns_limit_k_min       -59
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            53933
_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         28.995
_diffrn_reflns_theta_min         1.830
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.41
_diffrn_source_power             0.0705
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.984
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1091 before and 0.0707 after correction.
The Ratio of minimum to maximum transmission is 0.7983.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.488
_exptl_crystal_description       block
_exptl_crystal_F_000             7308
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   0.716
_exptl_transmission_factor_min   0.647
_refine_diff_density_max         1.179
_refine_diff_density_min         -1.007
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     432
_refine_ls_number_reflns         9491
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0406
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0263P)^2^+60.9707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0872
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7826
_reflns_number_total             9491
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02173h7.cif
_cod_data_source_block           1_a
_cod_depositor_comments
'Adding full bibliography for 1572545--1572551.cif.'
_cod_original_cell_volume        16098.4(8)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1572551
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.716
_shelx_estimated_absorpt_t_min   0.647
_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:
 C28(H28), C31(H31)
2.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C15(H15), C3(H3), C17(H17), C16(H16), C4(H4), C11(H11), C10(H10),
 C5(H5), C18(H18), C8(H8), C24(H24), C26(H26), C9(H9), C41(H41), C25(H25),
 C37(H37), C38(H38), C39(H39), C40(H40)
2.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C30(H30A,H30B,
 H30C), C42(H42A,H42B,H42C), C32(H32A,H32B,H32C), C29(H29A,H29B,H29C), C33(H33A,
 H33B,H33C)
;
_shelx_res_checksum              7692
_olex2_submission_special_instructions 'No special instructions were received'