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_1574714
_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         'C30 H59 Dy N4 O Si2'
_chemical_formula_sum            'C30 H59 Dy N4 O Si2'
_chemical_formula_weight         710.49
_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
_audit_creation_date             2024-07-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-01-26 deposited with the CCDC.	2025-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                92.672(3)
_cell_angle_beta                 111.785(2)
_cell_angle_gamma                95.539(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9353(7)
_cell_length_b                   12.8290(8)
_cell_length_c                   14.6085(11)
_cell_measurement_reflns_used    8622
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      22.78
_cell_measurement_theta_min      2.42
_cell_volume                     1886.6(2)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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  0.1225
_diffrn_reflns_av_unetI/netI     0.0688
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            61150
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.577
_diffrn_reflns_theta_min         2.099
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.069
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3851
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1571 before and 0.0879 after correction.
The Ratio of minimum to maximum transmission is 0.5165.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.251
_exptl_crystal_description       block
_exptl_crystal_F_000             738
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.032
_refine_diff_density_min         -1.136
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         8682
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0428P)^2^+1.6169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1128
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6709
_reflns_number_total             8682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01502b2.cif
_cod_data_source_block           1e
_cod_depositor_comments
'Adding full bibliography for 1574708--1574717.cif.'
_cod_database_code               1574714
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.733
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4A-C16A = N4-C16 = N4-C18 = N4A-C17A = N4-C17 = N4A-C18A
 1.47 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Si2 \\sim C24 \\sim C25 \\sim C26 \\sim C24A \\sim C25A \\sim C26A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O1 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C27A \\sim C28A \\sim C29A
\\sim C30A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C15 \\sim C16 \\sim C17 \\sim C18 \\sim N4 \\sim C16A \\sim C17A \\sim C18A
\\sim N4A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Same fragment restrains
{C15, C16A, C17A, C18A, N4A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C15, C16, C17, C18, N4}
{O1, C27A, C28A, C29A, C30A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{O1, C27, C28, C29, C30}
{Si2, C24A, C25A, C26A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{Si2, C24, C25, C26}
5. Others
 Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(N4A)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(N4)=FVAR(1)
 Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(2)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(2)
 Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=
 Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=1-FVAR(3)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B), C15(H15C,H15D),
 C16(H16A,H16B), C19(H19A,H19B), C23(H23A,H23B), C27(H27A,H27B), C28(H28A,H28B),
  C29(H29A,H29B), C30(H30A,H30B), C16A(H16C,H16D), C27A(H27C,H27D), C28A(H28C,
 H28D), C29A(H29C,H29D), C30A(H30C,H30D)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C24A(H24D,H24E,H24F), C25A(H25D,
 H25E,H25F), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              65396
_olex2_submission_special_instructions 'No special instructions were received'