Zinc substituted carbenes: synthesis, structure, and ambiphilic reactivity.
Jiang, Shengjie; Wang, Ganping; Cai, Yanping; Maron, Laurent; Xu, Xin; Chemical science 16 (2025) 15462–15468; doi:10.1039/d5sc03342j

data_1575219
_publ_section_title
;
 Zinc substituted carbenes: synthesis, structure, and ambiphilic
 reactivity.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              15462
_journal_page_last               15468
_journal_paper_doi               10.1039/d5sc03342j
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C64 H86 N8 P Zn, 0.5(C7 H8), 0.5(C6 H14)'
_chemical_formula_sum            'C70.5 H97 N8 P Zn'
_chemical_formula_weight         1152.90
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-14 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.3690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.5888(10)
_cell_length_b                   17.4697(8)
_cell_length_c                   19.2725(8)
_cell_measurement_reflns_used    9865
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      26.62
_cell_measurement_theta_min      2.24
_cell_volume                     7174.9(5)
_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      150(1)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1549
_diffrn_reflns_av_unetI/netI     0.1058
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            103376
_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         27.495
_diffrn_reflns_theta_min         2.124
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.407
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4190
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1572 before and 0.1118 after correction.
The Ratio of minimum to maximum transmission is 0.5620.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.067
_exptl_crystal_description       block
_exptl_crystal_F_000             2484
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.087
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     768
_refine_ls_number_reflns         16430
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.1735
_refine_ls_R_factor_gt           0.1092
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0962P)^2^+27.0714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2463
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10420
_reflns_number_total             16430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03342j2.cif
_cod_data_source_block           Complex_6
_cod_depositor_comments
'Adding full bibliography for 1575210--1575219.cif.'
_cod_original_formula_sum        'C70.50 H97 N8 P Zn'
_cod_database_code               1575219
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Restrained distances
 C80-C79
 1.51 with sigma of 0.02
 C79-C82 = C79-C81 = C78-C83
 1.39 with sigma of 0.02
 C82-C78 = C83-C65 = C65-C81
 1.38 with sigma of 0.02
 C66-C67 = C67-C68 = C68-C69 = C69-C70 = C70-C71
 1.52 with sigma of 0.02
 C72-C73 = C73-C74 = C74-C75 = C75-C76 = C76-C77
 1.52 with sigma of 0.02
 C79-C80
 1.52 with sigma of 0.01
 C80-C82 = C80-C81
 2.52 with sigma of 0.04
 C79-C78
 2.42 with sigma of 0.04
 C79-C65
 2.41 with sigma of 0.04
 C82-C83
 2.39 with sigma of 0.04
 C78-C65 = C83-C81
 2.4 with sigma of 0.04
 C66-C68 = C69-C71
 2.53 with sigma of 0.04
 C67-C69 = C68-C70
 2.54 with sigma of 0.04
 C72-C74 = C75-C77
 2.53 with sigma of 0.04
 C73-C75 = C74-C76
 2.54 with sigma of 0.04
 C79-C82 \\sim C82-C78 \\sim C78-C83 \\sim C83-C65 \\sim C65-C81 \\sim C81-C79
 with sigma of 0.02
 C79-C65 \\sim C79-C78 \\sim C81-C83 \\sim C82-C81 \\sim C78-C65 \\sim C82-C83
 with sigma of 0.04
 C80-C81 \\sim C80-C82
 with sigma of 0.04
 C66-C67 \\sim C67-C68 \\sim C68-C69 \\sim C69-C70 \\sim C70-C71
 with sigma of 0.02
 C66-C68 \\sim C68-C70 \\sim C67-C69 \\sim C69-C71
 with sigma of 0.04
 C72-C73 \\sim C73-C74 \\sim C74-C75 \\sim C75-C76 \\sim C76-C77
 with sigma of 0.02
 C72-C74 \\sim C74-C76 \\sim C73-C75 \\sim C75-C77
 with sigma of 0.04
2. Restrained planarity
 C80, C79, C82, C78, C83, C65, C81
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C80 \\sim C79 \\sim C82 \\sim C78 \\sim C83 \\sim C65 \\sim C81: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C80, C79, C82, C78, C83, C65, C81
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C66, C67, C68, C69, C70, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72, C73, C74, C75, C76, C77
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C80(0.5) H80A(0.5) H80B(0.5) H80C(0.5) C79(0.5) C82(0.5) H82(0.5)
 C78(0.5) H78(0.5) C83(0.5) H83(0.5) C65(0.5) H65(0.5) C81(0.5) H81(0.5)
 C66(0.25) H66A(0.25) H66B(0.25) H66C(0.25) C67(0.25) H67A(0.25) H67B(0.25)
 C68(0.25) H68A(0.25) H68B(0.25) C69(0.25) H69B(0.25) H69A(0.25) C70(0.25)
 H70A(0.25) H70B(0.25) C71(0.25) H71A(0.25) H71B(0.25) H71C(0.25) C72(0.25)
 H72A(0.25) H72B(0.25) H72C(0.25) C73(0.25) H73A(0.25) H73B(0.25) C74(0.25)
 H74A(0.25) H74B(0.25) C75(0.25) H75B(0.25) H75A(0.25) C76(0.25) H76A(0.25)
 H76B(0.25) C77(0.25) H77A(0.25) H77B(0.25) H77C(0.25)
6.a Ternary CH refined with riding coordinates:
 C45(H45), C36(H36), C48(H48), C33(H33)
6.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C67(H67A,H67B), C68(H68A,H68B), C69(H69B,
 H69A), C70(H70A,H70B), C73(H73A,H73B), C74(H74A,H74B), C75(H75B,H75A),
 C76(H76A,H76B)
6.c Aromatic/amide H refined with riding coordinates:
 C58(H58), C41(H41), C42(H42), C4(H4), C61(H61), C29(H29), C43(H43), C18(H18),
 C54(H54), C9(H9), C62(H62), C31(H31), C30(H30), C20(H20), C51(H51), C55(H55),
 C52(H52), C11(H11), C82(H82), C78(H78), C83(H83), C65(H65), C81(H81)
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C47(H47A,H47B,H47C), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C),
 C24(H24A,H24B,H24C), C50(H50A,H50B,H50C), C22(H22A,H22B,H22C), C34(H34A,H34B,
 H34C), C49(H49A,H49B,H49C), C46(H46A,H46B,H46C), C38(H38A,H38B,H38C), C15(H15A,
 H15B,H15C), C57(H57A,H57B,H57C), C23(H23A,H23B,H23C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C56(H56A,H56B,H56C), C14(H14A,H14B,H14C), C64(H64A,H64B,
 H64C), C63(H63A,H63B,H63C), C80(H80A,H80B,H80C), C66(H66A,H66B,H66C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C77(H77A,H77B,H77C)
;
_shelx_res_checksum              51319
_olex2_submission_special_instructions 'No special instructions were received'