Unique selectivity of rare-earth metal ambiphilic carbenes towards organic molecules and novel reactivity patterns with isonitriles
Chai, Fuxiang; Wu, Weikang; Rajeshkumar, Thayalan; Huang, Zeming; Yuan, Qingbing; Wei, Yun; Maron, Laurent; Wang, Shaowu; Chemical Science 16 (2025) 11870–11887; doi:10.1039/D5SC01502B

data_1574717
_publ_section_title
;
 Unique selectivity of rare-earth metal ambiphilic carbenes towards
 organic molecules and novel reactivity patterns with isonitriles
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              11870
_journal_page_last               11887
_journal_paper_doi               10.1039/D5SC01502B
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '0.5(C48 H94 B20 Er2 N8 O2), C7 H8'
_chemical_formula_sum            'C31 H55 B10 Er N4 O'
_chemical_formula_weight         775.15
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-07-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-01-26 deposited with the CCDC.	2025-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.500(4)
_cell_length_b                   12.603(3)
_cell_length_c                   14.677(3)
_cell_measurement_reflns_used    9488
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      27.15
_cell_measurement_theta_min      2.51
_cell_volume                     3607.0(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1451
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            54383
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         2.089
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.359
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4070
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1525 before and 0.1163 after correction.
The Ratio of minimum to maximum transmission is 0.5459.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1580
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.141
_refine_diff_density_min         -1.557
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.345
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     456
_refine_ls_number_reflns         3329
_refine_ls_number_restraints     1153
_refine_ls_restrained_S_all      1.197
_refine_ls_R_factor_all          0.1584
_refine_ls_R_factor_gt           0.1478
_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^)+(0.0001P)^2^+113.0358P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2755
_refine_ls_wR_factor_ref         0.2815
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2946
_reflns_number_total             3329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01502b2.cif
_cod_data_source_block           2c
_cod_depositor_comments
'Adding full bibliography for 1574708--1574717.cif.'
_cod_original_cell_volume        3607.0(12)
_cod_database_code               1574717
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.663
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C9-C2
 1.5 with sigma of 0.01
 N1-C15 = N4-C10 = N4-C16 = N4-C17 = N3-C12 = N3-C13 = N3-C14 = N2-C11 = N2-C9
 = N2-C18
 1.47 with sigma of 0.01
 O1-C21 = O1-C24
 1.43 with sigma of 0.01
 C22-C21 = C23-C22 = C24-C23
 1.54 with sigma of 0.01
 O1-C22 = O1-C23
 2.426 with sigma of 0.02
 C21-C23 = C22-C24
 2.515 with sigma of 0.02
 C24-C21
 2.336 with sigma of 0.02
 C31-C30 \\sim C31-C26
 with sigma of 0.02
 C31A-C30A \\sim C31A-C26A
 with sigma of 0.02
 C9-C18 \\sim C9-C11 \\sim C18-C11
 with sigma of 0.02
 C16-C17 \\sim C16-C10 \\sim C17-C10
 with sigma of 0.02
 B6-B10 \\sim B5-B10 \\sim B9-B10 \\sim B8-B10 \\sim B7-B10 \\sim B8-B7 \\sim
B7-B2 \\sim B7-B1 \\sim B7-B6 ~
 B8-B2 \\sim B8-B3 \\sim B9-B8 \\sim B9-B3 \\sim B9-B4 \\sim B9-B5 \\sim B5-B4
\\sim B6-B1 \\sim B2-B1 \\sim B3-B2
 \\sim B4-B3
 with sigma of 0.02
 C19-B4 \\sim C19-B5 \\sim C19-B6 \\sim C19-B1
 with sigma of 0.02
 C20-B4 \\sim C20-B1 \\sim C20-B3 \\sim C20-B2
 with sigma of 0.02
3. Restrained planarity
 C30A, C25A, C29A, C31A, C26A, C28A, C27A
 with sigma of 0.01
 C30, C31, C25, C26, C29, C27, C28
 with sigma of 0.01
 C2, C1, C3, C4, C8, C9, C5, C6, C7, N1, C15
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C10) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.003 and
sigma for terminal atoms of 0.006
5. Others
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C25A)=Sof(C30A)=Sof(H30A)=
 Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(H28A)=Sof(C27A)=Sof(H27A)=Sof(C26A)=
 Sof(H26A)=0.5*(1-FVAR(2))
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C25)=Sof(C30)=Sof(H30)=Sof(C29)=
 Sof(H29)=Sof(C28)=Sof(H28)=Sof(C27)=Sof(H27)=Sof(C26)=Sof(H26)=0.5*FVAR(2)
 Fixed Sof: C2(0.5) C1(0.5) C3(0.5) C4(0.5) H4(0.5) C5(0.5) H5(0.5) C6(0.5)
 H6(0.5) C7(0.5) H7(0.5) C8(0.5) B2(0.5) H2(0.5) C24(0.5) H24A(0.5) H24B(0.5)
 O1(0.5) B1(0.5) H1(0.5) C22(0.5) H22A(0.5) H22B(0.5) B7(0.5) H7A(0.5) B6(0.5)
 H6A(0.5) C21(0.5) H21A(0.5) H21B(0.5) C9(0.5) H9A(0.5) H9B(0.5) C23(0.5)
 H23A(0.5) H23B(0.5) C11(0.5) H11A(0.5) H11B(0.5) N2(0.5) C18(0.5) H18A(0.5)
 H18B(0.5) H18C(0.5) B3(0.5) H3(0.5) B4(0.5) H4A(0.5) B9(0.5) H9(0.5) B5(0.5)
 H5A(0.5) N3(0.5) N4(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C13(0.5)
 H13A(0.5) H13B(0.5) H13C(0.5) C12(0.5) H12A(0.5) H12B(0.5) N1(0.5) C14(0.5)
 H14A(0.5) H14B(0.5) H14C(0.5) C17(0.5) H17A(0.5) H17B(0.5) H17C(0.5) C16(0.5)
 H16A(0.5) H16B(0.5) C15(0.5) H15A(0.5) H15B(0.5) C20(0.5) C19(0.5) B8(0.5)
 H8(0.5) B10(0.5) H10(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C22(H22A,H22B), C21(H21A,H21B), C9(H9A,H9B), C23(H23A,H23B),
 C11(H11A,H11B), C12(H12A,H12B), C16(H16A,H16B), C15(H15A,H15B)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C30(H30), C29(H29), C28(H28), C27(H27),
 C26(H26), C30A(H30A), C29A(H29A), C28A(H28A), C27A(H27A), C26A(H26A)
6.c Fitted hexagon refined as free rotating group:
 C3(C4,C5,C6,C7,C8), C25(C30,C29,C28,C27,C26), C25A(C30A,C29A,C28A,C27A,C26A)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C31A(H31D,H31E,H31F)
6.e Boron cage BH refined with riding coordinates:
 B2(H2), B1(H1), B7(H7A), B6(H6A), B3(H3), B4(H4A), B9(H9), B5(H5A), B8(H8),
 B10(H10)
;
_shelx_res_checksum              98228
_olex2_submission_special_instructions 'No special instructions were received'