Toward vanadium-mediated alkyne metathesis
Hernandez, Shirley; Krivovicheva, Vasilisa; Sousa-Silva, Adenilson; Solans-Monfort, Xavier; Bukhryakov, Konstantin V.; Chemical Science  (2026) –; doi:10.1039/D6SC01683A

data_1576940
_publ_section_title
;
 Toward vanadium-mediated alkyne metathesis.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              9132
_journal_page_last               9137
_journal_paper_doi               10.1039/d6sc01683a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C49 H69 N2 O S Si3 V'
_chemical_formula_sum            'C49 H69 N2 O S Si3 V'
_chemical_formula_weight         869.33
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_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             2025-10-06
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-06 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                79.778(2)
_cell_angle_beta                 77.4170(10)
_cell_angle_gamma                80.9740(10)
_cell_formula_units_Z            2
_cell_length_a                   11.33270(10)
_cell_length_b                   13.7549(3)
_cell_length_c                   16.4917(3)
_cell_measurement_reflns_used    24055
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.1500
_cell_measurement_theta_min      3.2840
_cell_volume                     2450.38(7)
_computing_cell_refinement       'CrysAlisPro 1.171.44.105a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.105a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.105a (Rigaku OD, 2025)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.951
_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    -28.00  22.00   0.50    0.68    --  -50.44  22.00 -82.00  100
  2  \w   -123.00 -42.00   0.50    0.68    --  -50.44 -22.00 111.00  162
  3  \w    -22.00  28.00   0.50    0.68    --   50.44 -22.00 111.00  100
  4  \w     43.00 123.00   0.50    0.68    --   50.44  22.00 -82.00  160
  5  \w   -163.00 -81.00   0.50    2.70    --  -90.00 -22.00 111.00  164
  6  \w    102.00 178.00   0.50    2.70    --  110.69  22.00 -82.00  152
  7  \w    -93.00 -22.00   0.50    0.68    --  -50.44 134.00  46.72  142
  8  \w    -26.00  23.00   0.50    0.68    --  -50.44  19.00  30.00   98
  9  \w    -63.00  22.00   0.50    0.68    --  -50.44  57.00 -60.00  170
 10  \w    -26.00  23.00   0.50    0.68    --  -50.44  19.00  60.00   98
 11  \w    -26.00  23.00   0.50    0.68    --  -50.44  19.00-180.00   98
 12  \w     43.00 122.00   0.50    0.68    --   50.44  38.00-180.00  158
 13  \w     43.00 122.00   0.50    0.68    --   50.44  38.00-180.00  158
 14  \w   -161.00-103.00   0.50    2.70    --  -90.00 -57.00  60.00  116
 15  \w   -161.00-110.00   0.50    2.70    --  -90.00 -77.00-150.00  102
 16  \w   -162.00 -82.00   0.50    2.70    --  -90.00 -19.00-150.00  160
 17  \w   -159.00 -94.00   0.50    2.70    --  -90.00-125.00 -60.00  130
 18  \w   -162.00 -82.00   0.50    2.70    --  -90.00 -19.00-150.00  160
 19  \w   -162.00 -83.00   0.50    2.70    --  -90.00 -34.00 165.99  158
 20  \w    -66.00 -18.00   0.50    2.70    --  -90.00  57.00 -90.00   96
 21  \w   -161.00-110.00   0.50    2.70    --  -90.00 -77.00  30.00  102
 22  \w   -160.00-106.00   0.50    2.70    --  -90.00 -99.00-120.00  108
 23  \w    -66.00 -18.00   0.50    2.70    --  -90.00  57.00-120.00   96
 24  \w     42.00 111.00   0.50    2.70    --  110.69-125.00  30.00  138
 25  \w     42.00 111.00   0.50    2.70    --  110.69-125.00  30.00  138
 26  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00-120.00  130
 27  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00  30.00  130
 28  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00 -60.00  130
 29  \w     39.00  66.00   0.50    2.70    --  110.69 -57.00  60.00   54
 30  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00-150.00  130
 31  \w    103.00 178.00   0.50    2.70    --  110.69  57.00 120.00  150
 32  \w     39.00  66.00   0.50    2.70    --  110.69 -57.00-120.00   54
 33  \w     42.00 111.00   0.50    2.70    --  110.69-125.00   0.00  138
 34  \w     39.00 105.00   0.50    2.70    --  110.69 -77.00  30.00  132
 35  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00 150.00  130
 36  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00 120.00  130
 37  \w     39.00 105.00   0.50    2.70    --  110.69 -77.00  30.00  132
 38  \w     39.00  66.00   0.50    2.70    --  110.69 -57.00  30.00   54
 39  \w     39.00  66.00   0.50    2.70    --  110.69 -57.00 -90.00   54
 40  \w     41.00 106.00   0.50    2.70    --  110.69 -99.00-180.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1376205000
_diffrn_orient_matrix_UB_12      0.0076884000
_diffrn_orient_matrix_UB_13      -0.0266497000
_diffrn_orient_matrix_UB_21      0.0245164000
_diffrn_orient_matrix_UB_22      -0.1120362000
_diffrn_orient_matrix_UB_23      -0.0063589000
_diffrn_orient_matrix_UB_31      -0.0125791000
_diffrn_orient_matrix_UB_32      0.0232425000
_diffrn_orient_matrix_UB_33      -0.0928303000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            46608
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.223
_diffrn_reflns_theta_min         3.290
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.059
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94180
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.105a (Rigaku Oxford Diffraction, 2025)
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    1.178
_exptl_crystal_description       block
_exptl_crystal_F_000             932
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether at --35?'
_exptl_crystal_size_max          0.139
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.504
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         10103
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0449P)^2^+1.0395P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0911
_refine_ls_wR_factor_ref         0.0932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9176
_reflns_number_total             10103
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01683a3.cif
_cod_data_source_block           vk_393
_cod_depositor_comments
'Adding full bibliography for 1576939--1576943.cif.'
_cod_original_cell_volume        2450.39(8)
_cod_database_code               1576940
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'V Si2 N2 C30 H50 O2 S'
_shelx_estimated_absorpt_t_max   0.852
_shelx_estimated_absorpt_t_min   0.676
_diffrn_oxdiff_digest_hkl
;
433abab8f344556473542b8198017b598bebb5
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(Si3)
2.a Ternary CH refined with riding coordinates:
 C41(H41), C44(H44), C47(H47)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C11(H11), C13(H13), C14(H14), C6(H6), C5(H5), C30(H30), C28(H28),
 C40(H40), C24(H24), C34(H34), C27(H27), C26(H26), C36(H36), C31(H31), C32(H32),
  C25(H25), C33(H33), C39(H39), C37(H37), C38(H38)
2.c Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C43(H43A,H43B,
 H43C), C48(H48A,H48B,H48C), C46(H46A,H46B,H46C), C17(H17A,H17B,H17C), C42(H42A,
 H42B,H42C), C45(H45A,H45B,H45C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C22(H22A,
 H22B,H22C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              89861
_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 1.132
_oxdiff_exptl_absorpt_empirical_full_min 0.877