CO methylenation mediated by organo-alkali metal reagents: metal identity and ligand effects
Yang, Xiao; Davison, Nathan; Lowe, Matthew E.; Waddell, Paul G.; Armstrong, Roly J.; McMullin, Claire L.; Hopkinson, Matthew N.; Lu, Erli; Chemical Science 16 (2025) 11151–11160; doi:10.1039/D5SC02313K

data_1574668
_publ_section_title
;
 C&#xE001;O methylenation mediated by organo-alkali metal reagents: metal
 identity and ligand effects
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              11151
_journal_page_last               11160
_journal_paper_doi               10.1039/D5SC02313K
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C68 H84 K4 O4 Si4, 2(C7 H14)'
_chemical_formula_sum            'C82 H112 K4 O4 Si4'
_chemical_formula_weight         1430.47
_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             2023-09-12
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2025-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                100.8590(10)
_cell_angle_beta                 90.4230(10)
_cell_angle_gamma                94.8410(10)
_cell_formula_units_Z            2
_cell_length_a                   12.8781(2)
_cell_length_b                   16.8307(2)
_cell_length_c                   19.5417(2)
_cell_measurement_reflns_used    26245
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      75.2580
_cell_measurement_theta_min      2.2870
_cell_volume                     4143.76(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.937
_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    -23.00 129.00   0.50    6.19    --   46.10  18.00-142.00  304
  2  \w    -36.00  26.00   0.50    6.19    --   46.10 -18.00  49.00  124
  3  \w   -129.00  22.00   0.50    6.19    --  -46.98 -18.00  49.00  302
  4  \w   -175.00 -23.00   0.50    6.19    --  -92.45 -18.00  49.00  304
  5  \w     28.00 178.00   0.50    6.19    --   97.10  18.00-142.00  300
  6  \w     39.00 178.00   0.50    6.19    --  108.07  18.00-142.00  278
  7  \w    -48.00 -12.00   0.50    6.19    --   10.00 124.00 -76.81   72
  8  \w    -44.00 -13.00   0.50    6.19    --   14.00 125.00-146.04   62
  9  \w    -26.00  36.00   0.50    6.19    --  -46.98  18.00-142.00  124
 10  \w     16.00  43.00   0.50    6.19    --   50.00  82.00  61.30   54
 11  \w     13.00  43.00   0.50    6.19    --   50.00  88.00-174.94   60
 12  \w     17.00  43.00   0.50    6.19    --   50.00  80.00-120.87   52
 13  \w     17.00  43.00   0.50    6.19    --   50.00  80.00  87.54   52
 14  \w     17.00  43.00   0.50    6.19    --   50.00  80.00 -90.01   52
 15  \w     17.00  43.00   0.50    6.19    --   54.00  87.00 121.50   52
 16  \w     27.00 129.00   0.50    6.19    --   58.00  77.00 -88.54  204
 17  \w   -105.00 -22.00   0.50    6.19    --  -92.45  77.00 150.00  166
 18  \w   -105.00 -22.00   0.50    6.19    --  -92.45  77.00   0.00  166
 19  \w   -112.00 -16.00   0.50    6.19    --  -92.45 125.00 -90.00  192
 20  \w    -71.00 -15.00   0.50    6.19    --  -92.45  61.00 -90.00  112
 21  \w   -112.00 -16.00   0.50    6.19    --  -92.45 125.00 150.00  192
 22  \w    -51.00 -11.00   0.50    6.19    --  -92.45  45.00  60.00   80
 23  \w     20.00  71.00   0.50    6.19    --   97.10 -61.00-120.00  102
 24  \w     24.00 105.00   0.50    6.19    --   97.10 -95.00-120.00  162
 25  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00  30.00   70
 26  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00 -90.00   70
 27  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00 -60.00   70
 28  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00  90.00   70
 29  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00-120.00   70
 30  \w     24.00 105.00   0.50    6.19    --   97.10 -95.00   0.00  162
 31  \w     16.00  51.00   0.50    6.19    --   97.10 -45.00 -30.00   70
 32  \w     20.00  71.00   0.50    6.19    --   97.10 -61.00 -30.00  102
 33  \w   -124.00 -24.00   0.50    6.19    --  -99.00 141.00  73.31  200
 34  \w   -122.00 -23.00   0.50    6.19    --  -99.00 139.00 -45.73  198
 35  \w   -121.00 -23.00   0.50    6.19    --  -99.00 138.00-172.81  196
 36  \w     38.00 105.00   0.50    6.19    --  108.07 -77.00 150.00  134
 37  \w     83.00 178.00   0.50    6.19    --  108.07  61.00 -90.00  190
 38  \w     35.00 105.00   0.50    6.19    --  108.07 -95.00  90.00  140
 39  \w     32.00  71.00   0.50    6.19    --  108.07 -61.00  30.00   78
 40  \w     41.00  67.00   0.50    6.19    --  108.07 -61.00 -90.00   52
 41  \w     86.00 112.00   0.50    6.19    --  108.07-125.00 120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0998400000
_diffrn_orient_matrix_UB_12      -0.0397799000
_diffrn_orient_matrix_UB_13      0.0131934000
_diffrn_orient_matrix_UB_21      0.0667036000
_diffrn_orient_matrix_UB_22      0.0753816000
_diffrn_orient_matrix_UB_23      -0.0140291000
_diffrn_orient_matrix_UB_31      -0.0019516000
_diffrn_orient_matrix_UB_32      0.0385811000
_diffrn_orient_matrix_UB_33      0.0779508000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            76812
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.781
_diffrn_reflns_theta_min         2.303
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.806
_exptl_absorpt_correction_T_max  0.869
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.146
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.340
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.00017(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     990
_refine_ls_number_reflns         16585
_refine_ls_number_restraints     1767
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0533P)^2^+2.2175P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1157
_refine_ls_wR_factor_ref         0.1210
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14077
_reflns_number_total             16585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02313k2.cif
_cod_data_source_block           elu230014_fa
_cod_depositor_comments
'Adding full bibliography for 1574667--1574668.cif.'
_cod_database_code               1574668
_chemical_oxdiff_formula         'C17 H21 K1 O1 Si1'
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.662
_diffrn_oxdiff_digest_frames
;
01bb0bcc8167b7cc640a382ea34b35f9090549221ab
;
_diffrn_oxdiff_digest_hkl
;
014adfb70d84d1cb49ab47aaa7626bf2444662
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C77A-C78A \\sim C81B-C80B
 with sigma of 0.02
 C80A-C76A \\sim C78B-C76B
 with sigma of 0.04
 C77A-C76A \\sim C81B-C76B
 with sigma of 0.02
 C81A-C79A \\sim C77B-C79B
 with sigma of 0.04
 C81A-C80A \\sim C77B-C78B
 with sigma of 0.02
 C81A-C76A \\sim C77B-C76B
 with sigma of 0.02
 C80A-C79A \\sim C78B-C79B
 with sigma of 0.02
 C78A-C79A \\sim C80B-C79B
 with sigma of 0.02
 C81A-C82A \\sim C77B-C82B
 with sigma of 0.04
 C76A-C82A \\sim C76B-C82B
 with sigma of 0.02
 C80A-C78A \\sim C78B-C80B
 with sigma of 0.04
 C78A-C76A \\sim C80B-C76B
 with sigma of 0.04
 C77A-C81A \\sim C81B-C77B
 with sigma of 0.04
 C77A-C79A \\sim C81B-C79B
 with sigma of 0.04
 C77A-C82A \\sim C81B-C82B
 with sigma of 0.04
 C74A-C69A \\sim C70B-C69B
 with sigma of 0.02
 C74A-C73A \\sim C70B-C71B
 with sigma of 0.02
 C74A-C72A \\sim C70B-C72B
 with sigma of 0.04
 C69A-C73A \\sim C69B-C71B
 with sigma of 0.04
 C70A-C75A \\sim C74B-C75B
 with sigma of 0.04
 C73A-C71A \\sim C71B-C73B
 with sigma of 0.04
 C70A-C69A \\sim C74B-C69B
 with sigma of 0.02
 C70A-C71A \\sim C74B-C73B
 with sigma of 0.02
 C74A-C70A \\sim C70B-C74B
 with sigma of 0.04
 C74A-C75A \\sim C70B-C75B
 with sigma of 0.04
 C69A-C75A \\sim C69B-C75B
 with sigma of 0.02
 C70A-C72A \\sim C74B-C72B
 with sigma of 0.04
 C69A-C71A \\sim C69B-C73B
 with sigma of 0.04
 C73A-C72A \\sim C71B-C72B
 with sigma of 0.02
 C71A-C72A \\sim C73B-C72B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C76A \\sim C77A \\sim C78A \\sim C79A \\sim C80A \\sim C81A \\sim C82A \\sim
C76B \\sim C77B \\sim C78B \\sim C79B \\sim C80B \\sim C81B \\sim C82B: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C69A \\sim C70A \\sim C71A \\sim C72A \\sim C73A \\sim C74A \\sim C75A \\sim
C69B \\sim C70B \\sim C71B \\sim C72B \\sim C73B \\sim C74B \\sim C75B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C69A(0.87924) H69A(0.87924) C70A(0.87924) H70A(0.87924)
 H70B(0.87924) C71A(0.87924) H71A(0.87924) H71B(0.87924) C72A(0.87924)
 H72A(0.87924) H72B(0.87924) C73A(0.87924) H73A(0.87924) H73B(0.87924)
 C74A(0.87924) H74A(0.87924) H74B(0.87924) C75A(0.87924) H75A(0.87924)
 H75B(0.87924) H75C(0.87924) C76A(0.92617) H76A(0.92617) C77A(0.92617)
 H77A(0.92617) H77B(0.92617) C78A(0.92617) H78A(0.92617) H78B(0.92617)
 C79A(0.92617) H79A(0.92617) H79B(0.92617) C80A(0.92617) H80A(0.92617)
 H80B(0.92617) C81A(0.92617) H81A(0.92617) H81B(0.92617) C82A(0.92617)
 H82A(0.92617) H82B(0.92617) H82C(0.92617) C69B(0.12076) H69B(0.12076)
 C70B(0.12076) H70C(0.12076) H70D(0.12076) C71B(0.12076) H71C(0.12076)
 H71D(0.12076) C72B(0.12076) H72C(0.12076) H72D(0.12076) C73B(0.12076)
 H73C(0.12076) H73D(0.12076) C74B(0.12076) H74C(0.12076) H74D(0.12076)
 C75B(0.12076) H75D(0.12076) H75E(0.12076) H75F(0.12076) C76B(0.07383)
 H76B(0.07383) C77B(0.07383) H77C(0.07383) H77D(0.07383) C78B(0.07383)
 H78C(0.07383) H78D(0.07383) C79B(0.07383) H79C(0.07383) H79D(0.07383)
 C80B(0.07383) H80C(0.07383) H80D(0.07383) C81B(0.07383) H81C(0.07383)
 H81D(0.07383) C82B(0.07383) H82D(0.07383) H82E(0.07383) H82F(0.07383)
6.a Ternary CH refined with riding coordinates:
 C69A(H69A), C76A(H76A), C69B(H69B), C76B(H76B)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C31(H31A,H31B), C48(H48A,H48B), C65(H65A,H65B), C70A(H70A,
 H70B), C71A(H71A,H71B), C72A(H72A,H72B), C73A(H73A,H73B), C74A(H74A,H74B),
 C77A(H77A,H77B), C78A(H78A,H78B), C79A(H79A,H79B), C80A(H80A,H80B), C81A(H81A,
 H81B), C70B(H70C,H70D), C71B(H71C,H71D), C72B(H72C,H72D), C73B(H73C,H73D),
 C74B(H74C,H74D), C77B(H77C,H77D), C78B(H78C,H78D), C79B(H79C,H79D), C80B(H80C,
 H80D), C81B(H81C,H81D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C37(H37), C38(H38), C39(H39), C40(H40),
 C41(H41), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C54(H54), C55(H55),
  C56(H56), C57(H57), C58(H58), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C),
 C68(H68A,H68B,H68C), C75A(H75A,H75B,H75C), C82A(H82A,H82B,H82C), C75B(H75D,
 H75E,H75F), C82B(H82D,H82E,H82F)
;
_shelx_res_checksum              82002
_shelx_shelxl_version_number     2019/1
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.492
_oxdiff_exptl_absorpt_empirical_full_min 0.592