CO<sub>2</sub> hydrosilylation catalyzed by an N-heterocyclic carbene (NHC)-stabilized stannyliumylidene.
Niu, Dechuang; Kostenko, Arseni; Kelly, John A.; Sarkar, Debotra; Xu, Huihui; Inoue, Shigeyoshi; Chemical science 16 (2025) 4014–4022; doi:10.1039/d4sc07116f

data_1573734
_publ_section_title
;
 CO<sub>2</sub> hydrosilylation catalyzed by an N-heterocyclic carbene
 (NHC)-stabilized stannyliumylidene.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              4014
_journal_page_last               4022
_journal_paper_doi               10.1039/d4sc07116f
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C40 H49 N4 O4 Sn, C32 H12 B F24'
_chemical_formula_sum            'C72 H61 B F24 N4 O4 Sn'
_chemical_formula_weight         1631.74
_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             2023-04-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-11 deposited with the CCDC.	2025-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                109.831(2)
_cell_angle_beta                 92.107(2)
_cell_angle_gamma                102.860(2)
_cell_formula_units_Z            2
_cell_length_a                   10.4739(5)
_cell_length_b                   16.0890(8)
_cell_length_c                   23.3384(11)
_cell_measurement_reflns_used    9601
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.39
_cell_measurement_theta_min      2.32
_cell_volume                     3579.7(3)
_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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_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  0.0252
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            66144
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         1.932
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.471
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.7055
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0809 before and 0.0415 after correction.
The Ratio of minimum to maximum transmission is 0.9467.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_description       fragment
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.347
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.106
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.520
_refine_diff_density_rms         0.052
_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     1206
_refine_ls_number_reflns         13105
_refine_ls_number_restraints     737
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0269P)^2^+4.1014P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12278
_reflns_number_total             13105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07116f2.cif
_cod_data_source_block           mo_niude13_0m
_cod_depositor_comments
'Adding full bibliography for 1573732--1573734.cif.'
_cod_database_code               1573734
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.854
_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
 F1-C47 \\sim F1A-C47
 with sigma of 0.02
 F2-C47 \\sim F2A-C47
 with sigma of 0.02
 F3-C47 \\sim F3A-C47
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1D \\sim N2D \\sim C25D \\sim C26D \\sim C27D \\sim C28D \\sim C29D \\sim C30D
\\sim C31D \\sim N1 \\sim N2 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29
\\sim C30 \\sim C31: within 2A with sigma of 0.001 and sigma for terminal atoms
of 0.002 within 2A
N3D \\sim N4D \\sim C32D \\sim C33D \\sim C34D \\sim C35D \\sim C36D \\sim C37D
\\sim C38D \\sim N3 \\sim N4 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36
\\sim C37 \\sim C38: within 2A with sigma of 0.001 and sigma for terminal atoms
of 0.002 within 2A
C56D \\sim F10D \\sim F11D \\sim F12D \\sim C56 \\sim F10 \\sim F11 \\sim F12:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
4. Same fragment restrains
{C56D, F10D, F11D, F12D, C56, F10, F11, F12} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C56, F10, F11, F12, C56D, F10D, F11D, F12D}
{N3D, N4D, C32D, C33D, C34D, C35D, C36D, C37D, C38D, N3, N4, C32, C33, C34,
C35, C36, C37, C38} sigma for 1-2: 0.001, 1-3: 0.04
as in
{N3, N4, C32, C33, C34, C35, C36, C37, C38, N3D, N4D, C32D, C33D, C34D, C35D,
C36D, C37D, C38D}
{N1D, N2D, C25D, C26D, C27D, C28D, C29D, C30D, C31D, N1, N2, C25, C26, C27,
C28, C29, C30, C31} sigma for 1-2: 0.001, 1-3: 0.04
as in
{N1, N2, C25, C26, C27, C28, C29, C30, C31, N1D, N2D, C25D, C26D, C27D, C28D,
C29D, C30D, C31D}
5. Others
 Sof(N1D)=Sof(N2D)=Sof(C25D)=Sof(C26D)=Sof(C27D)=Sof(C28D)=Sof(H28d)=Sof(H28e)=
 Sof(H28f)=Sof(C29D)=Sof(H29d)=Sof(H29e)=Sof(H29f)=Sof(C30D)=Sof(H30d)=
 Sof(H30e)=Sof(H30f)=Sof(C31D)=Sof(H31d)=Sof(H31e)=Sof(H31f)=1-FVAR(1)
 Sof(N1)=Sof(N2)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(C28)=Sof(H28a)=Sof(H28b)=
 Sof(H28c)=Sof(C29)=Sof(H29a)=Sof(H29b)=Sof(H29c)=Sof(C30)=Sof(H30a)=Sof(H30b)=
 Sof(H30c)=Sof(C31)=Sof(H31a)=Sof(H31b)=Sof(H31c)=FVAR(1)
 Sof(N3D)=Sof(N4D)=Sof(C32D)=Sof(C33D)=Sof(C34D)=Sof(C35D)=Sof(H35d)=Sof(H35e)=
 Sof(H35f)=Sof(C36D)=Sof(H36d)=Sof(H36e)=Sof(H36f)=Sof(C37D)=Sof(H37d)=
 Sof(H37e)=Sof(H37f)=Sof(C38D)=Sof(H38d)=Sof(H38e)=Sof(H38f)=1-FVAR(2)
 Sof(N3)=Sof(N4)=Sof(C32)=Sof(C33)=Sof(C34)=Sof(C35)=Sof(H35a)=Sof(H35b)=
 Sof(H35c)=Sof(C36)=Sof(H36a)=Sof(H36b)=Sof(H36c)=Sof(C37)=Sof(H37a)=Sof(H37b)=
 Sof(H37c)=Sof(C38)=Sof(H38a)=Sof(H38b)=Sof(H38c)=FVAR(2)
 Sof(C56D)=Sof(F10D)=Sof(F11D)=Sof(F12D)=1-FVAR(3)
 Sof(C56)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(F2A)=Sof(F1A)=Sof(F3A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C18(H18), C20(H20), C42(H42),
 C44(H44), C46(H46), C50(H50), C52(H52), C54(H54), C58(H58), C60(H60), C62(H62),
  C66(H66), C68(H68), C70(H70)
6.b Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C14(H14a,H14b,H14c), C15(H15a,H15b,H15c), C22(H22a,H22b,
 H22c), C23(H23a,H23b,H23c), C24(H24a,H24b,H24c), C28(H28a,H28b,H28c), C29(H29a,
 H29b,H29c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c), C28D(H28d,H28e,H28f),
 C29D(H29d,H29e,H29f), C30D(H30d,H30e,H30f), C31D(H31d,H31e,H31f), C35(H35a,
 H35b,H35c), C36(H36a,H36b,H36c), C37(H37a,H37b,H37c), C38(H38a,H38b,H38c),
 C35D(H35d,H35e,H35f), C36D(H36d,H36e,H36f), C37D(H37d,H37e,H37f), C38D(H38d,
 H38e,H38f)
;
_shelx_res_checksum              20583
_olex2_submission_special_instructions 'No special instructions were received'