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_1575211
_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         'C50 H67 N4 P Zn, 0.5(C6 H14)'
_chemical_formula_sum            'C53 H74 N4 P Zn'
_chemical_formula_weight         863.50
_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             2024-09-10
_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                70.153(7)
_cell_angle_beta                 76.765(5)
_cell_angle_gamma                79.146(5)
_cell_formula_units_Z            2
_cell_length_a                   13.2792(7)
_cell_length_b                   13.7788(10)
_cell_length_c                   15.3972(12)
_cell_measurement_reflns_used    8437
_cell_measurement_temperature    223.00(10)
_cell_measurement_theta_max      26.4390
_cell_measurement_theta_min      1.9520
_cell_volume                     2560.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      223.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4471
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.856
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -62.00  37.00   1.00    1.50    --   12.87 -37.00 -60.00   99
  2  \w    -11.00  76.00   1.00    1.50    --   12.87  37.00 120.00   87
  3  \w    -19.00  33.00   1.00    1.50    --   12.87 -77.00-180.00   52
  4  \w    -31.00  16.00   1.00    1.50    --  -13.65 -77.00-180.00   47
  5  \w    -16.00  22.00   1.00    1.50    --  -13.65 -99.00-120.00   38
  6  \w    -13.00  18.00   1.00    1.50    --  -13.65 -99.00  90.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0157577000
_diffrn_orient_matrix_UB_12      0.0310251000
_diffrn_orient_matrix_UB_13      0.0304085000
_diffrn_orient_matrix_UB_21      0.0364699000
_diffrn_orient_matrix_UB_22      -0.0314466000
_diffrn_orient_matrix_UB_23      0.0284254000
_diffrn_orient_matrix_UB_31      0.0384330000
_diffrn_orient_matrix_UB_32      0.0329854000
_diffrn_orient_matrix_UB_33      -0.0272947000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0878
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.856
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26552
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.856
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.452
_diffrn_reflns_theta_min         1.587
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.547
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71284
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_description       block
_exptl_crystal_F_000             930
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     573
_refine_ls_number_reflns         13321
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1113
_refine_ls_R_factor_gt           0.0586
_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^)+(0.0620P)^2^+0.1299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1630
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7913
_reflns_number_total             13321
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03342j2.cif
_cod_data_source_block           Complex_2b
_cod_depositor_comments
'Adding full bibliography for 1575210--1575219.cif.'
_cod_database_code               1575211
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     CHNZnP
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.908
_olex2_refinement_description
;
1. Restrained distances
 C51A-C52A = C52A-C53A = C53A-C54A = C54A-C55A = C55A-C1F
 1.52 with sigma of 0.02
 C51-C52 = C52-C53 = C53-C54 = C54-C55 = C55-C56
 1.52 with sigma of 0.02
 C51A-C53A = C54A-C1F
 2.53 with sigma of 0.04
 C52A-C54A = C53A-C55A
 2.54 with sigma of 0.04
 C51-C53 = C54-C56
 2.53 with sigma of 0.04
 C52-C54 = C53-C55
 2.54 with sigma of 0.04
 C51A-C52A \\sim C52A-C53A \\sim C53A-C54A \\sim C54A-C55A \\sim C55A-C1F
 with sigma of 0.02
 C51A-C53A \\sim C53A-C55A \\sim C52A-C54A \\sim C54A-C1F
 with sigma of 0.04
 C51-C52 \\sim C52-C53 \\sim C53-C54 \\sim C54-C55 \\sim C55-C56
 with sigma of 0.02
 C51-C53 \\sim C53-C55 \\sim C52-C54 \\sim C54-C56
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55A \\sim C1F: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 C51A, C52A, C53A, C54A, C55A, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C51A(0.25) H51A(0.25) H51B(0.25) H51C(0.25) C52A(0.25) H52A(0.25)
 H52B(0.25) C53A(0.25) H53A(0.25) H53B(0.25) C54A(0.25) H54A(0.25) H54B(0.25)
 C55A(0.25) H55A(0.25) H55B(0.25) C1F(0.25) H1FA(0.25) H1FB(0.25) H1FC(0.25)
 C51(0.25) H51D(0.25) H51E(0.25) H51F(0.25) C52(0.25) H52C(0.25) H52D(0.25)
 C53(0.25) H53C(0.25) H53D(0.25) C54(0.25) H54C(0.25) H54D(0.25) C55(0.25)
 H55C(0.25) H55D(0.25) C56(0.25) H56A(0.25) H56B(0.25) H56C(0.25)
5.a Ternary CH refined with riding coordinates:
 C48(H48), C45(H45), C36(H36), C33(H33)
5.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C52A(H52A,H52B), C53A(H53A,H53B), C54A(H54A,
 H54B), C55A(H55A,H55B), C52(H52C,H52D), C53(H53C,H53D), C54(H54C,H54D),
 C55(H55C,H55D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C18(H18), C29(H29), C43(H43), C30(H30), C42(H42), C9(H9), C20(H20),
 C11(H11), C31(H31), C41(H41)
5.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C24(H24A,H24B,H24C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C6(H6A,H6B,H6C), C22(H22A,H22B,H22C), C47(H47A,H47B,H47C), C34(H34A,
 H34B,H34C), C46(H46A,H46B,H46C), C37(H37A,H37B,H37C), C14(H14A,H14B,H14C),
 C50(H50A,H50B,H50C), C38(H38A,H38B,H38C), C23(H23A,H23B,H23C), C49(H49A,H49B,
 H49C), C35(H35A,H35B,H35C), C51A(H51A,H51B,H51C), C1F(H1FA,H1FB,H1FC),
 C51(H51D,H51E,H51F), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              9558
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.368
_oxdiff_exptl_absorpt_empirical_full_min 0.726