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_1572547
_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         'C32 H45 Hf N3 Si'
_chemical_formula_sum            'C32 H45 Hf N3 Si'
_chemical_formula_weight         678.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-12-06
_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                 114.0880(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4880(3)
_cell_length_b                   38.1993(14)
_cell_length_c                   9.6016(3)
_cell_measurement_reflns_used    7777
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      28.26
_cell_measurement_theta_min      2.56
_cell_volume                     3176.92(18)
_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)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0513
_diffrn_reflns_av_unetI/netI     0.0850
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            31489
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.000
_diffrn_reflns_theta_min         2.557
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.345
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6393
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0924 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.8564.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   0.753
_exptl_transmission_factor_min   0.600
_refine_diff_density_max         1.614
_refine_diff_density_min         -1.244
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.239(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         16654
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0219P)^2^+2.2439P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0932
_reflns_Friedel_coverage         0.972
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                15277
_reflns_number_total             16654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02173h7.cif
_cod_data_source_block           a_a
_cod_depositor_comments
'Adding full bibliography for 1572545--1572551.cif.'
_cod_database_code               1572547
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.753
_shelx_estimated_absorpt_t_min   0.600
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.761(12)
 0.239(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C33A) = Uanis(C32A)
Uanis(C33) = Uanis(C32)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C24A(H24A), C27A(H27A)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C20(H20),
 C21(H21), C22(H22), C3A(H3A), C4A(H4A), C5A(H5A), C8A(H8A), C9A(H9A),
 C10A(H10A), C11A(H11A), C20A(H20A), C21A(H21A), C22A(H22A)
4.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C25A(H25D,
 H25E,H25F), C26A(H26D,H26E,H26F), C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F),
 C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F), C32A(H32D,H32E,H32F), C33A(H33D,
 H33E,H33F)
;
_shelx_res_checksum              24080
_olex2_submission_special_instructions 'No special instructions were received'