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_1572549
_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         'C36 H50 N4 Zr'
_chemical_formula_sum            'C36 H50 N4 Zr'
_chemical_formula_weight         630.02
_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             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                84.604(4)
_cell_angle_beta                 76.557(3)
_cell_angle_gamma                65.977(4)
_cell_formula_units_Z            2
_cell_length_a                   10.4428(7)
_cell_length_b                   12.0367(10)
_cell_length_c                   15.1051(10)
_cell_measurement_reflns_used    2705
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      25.30
_cell_measurement_theta_min      2.19
_cell_volume                     1686.7(2)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0613
_diffrn_reflns_av_unetI/netI     0.0928
_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       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            13141
_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         26.000
_diffrn_reflns_theta_min         1.852
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.355
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1114 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.8662.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.240
_exptl_crystal_description       block
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.109
_refine_diff_density_max         1.334
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         6606
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0611
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0599P)^2^+1.8009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1401
_refine_ls_wR_factor_ref         0.1538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5362
_reflns_number_total             6606
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02173h7.cif
_cod_data_source_block           q
_cod_depositor_comments
'Adding full bibliography for 1572545--1572551.cif.'
_cod_database_code               1572549
_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. Restrained distances
 C35-C34 = C35A-C34A = C36A-C34A = C36-C34
 1.51 with sigma of 0.02
 C32-C34 = C34A-C32A
 1.5 with sigma of 0.02
 N4-C32 = N4-C32A
 1.3 with sigma of 0.02
 C33-C32 = C33A-C32A
 1.5 with sigma of 0.02
 H33B-H35A
 2.2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C33) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C32)
\\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C35A) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C35A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C34A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C35A) = Uanis(C35)
Uanis(C33) = Uanis(C33A)
4. Others
 Fixed Sof: C32A(0.5) C34(0.5) H34(0.5) C34A(0.5) H34A(0.5) C35A(0.5)
 H35A(0.5) H35B(0.5) H35C(0.5) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C35(0.5)
 H35D(0.5) H35E(0.5) H35F(0.5) C36A(0.5) H36D(0.5) H36E(0.5) H36F(0.5) C32(0.5)
 C33A(0.5) H33A(0.5) H33B(0.5) H33C(0.5) C33(0.5) H33D(0.5) H33E(0.5) H33F(0.5)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C9(H9), C29(H29), C34(H34), C34A(H34A)
5.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C22(H22), C25(H25), C24(H24), C5(H5), C17(H17), C18(H18), C23(H23),
 C6(H6), C7(H7)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C28(H28A,H28B,H28C), C3(H3A,H3B,
 H3C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C35A(H35A,H35B,H35C), C36(H36A,H36B,H36C),
 C35(H35D,H35E,H35F), C36A(H36D,H36E,H36F), C33A(H33A,H33B,H33C), C33(H33D,H33E,
 H33F)
;
_shelx_res_checksum              2114
_olex2_submission_special_instructions 'No special instructions were received'