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_1576941
_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         'C48 H57 N2 O4 Si2 V'
_chemical_formula_sum            'C48 H57 N2 O4 Si2 V'
_chemical_formula_weight         833.07
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 114.0650(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2210(2)
_cell_length_b                   10.89970(10)
_cell_length_c                   20.6591(2)
_cell_measurement_reflns_used    22948
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.9930
_cell_measurement_theta_min      4.3500
_cell_volume                     4568.78(8)
_computing_cell_refinement       'CrysAlisPro 1.171.44.89a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.92a 64-bit (release 31-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.89a (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 0.975
_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    -71.00  22.00   0.50    2.55    --  -50.47  78.00-104.00  186
  2  \w    -20.00  71.00   0.50    2.55    --   50.47 -78.00 129.00  182
  3  \w   -110.00 -18.00   0.50   10.21    --  -90.00  78.00-104.00  184
  4  \w   -110.00 -18.00   0.50   10.21    --  -90.00  78.00-104.00  184
  5  \w     39.00 110.00   0.50   10.21    --  110.65 -78.00 129.00  142
  6  \w    122.00 173.00   0.50   10.21    --  110.65  78.00-104.00  102
  7  \w    -25.00  20.00   0.50    2.55    --  -50.47  19.00-180.00   90
  8  \w   -122.00 -43.00   0.50    2.55    --  -50.47 -38.00  60.00  158
  9  \w    -21.00  20.00   0.50    2.55    --   50.47 -19.00-120.00   82
 10  \w      0.00  25.00   0.50    2.55    --   50.47 -19.00-180.00   50
 11  \w     17.00  43.00   0.50    2.55    --   50.47 -38.00   0.00   52
 12  \w   -158.00-110.00   0.50   10.21    --  -90.00 -77.00 150.00   96
 13  \w   -148.00-123.00   0.50   10.21    --  -90.00 -57.00-120.00   50
 14  \w    -66.00 -24.00   0.50   10.21    --  -90.00  57.00-120.00   84
 15  \w    -62.00 -37.00   0.50   10.21    --  -90.00  57.00 150.00   50
 16  \w   -144.00-119.00   0.50   10.21    --  -90.00 -78.00 129.00   50
 17  \w    -64.00 -18.00   0.50   10.21    --  -90.00  57.00  90.00   92
 18  \w    104.00 172.00   0.50   10.21    --  110.65  19.00  90.00  136
 19  \w     39.00  66.00   0.50   10.21    --  110.65 -57.00-180.00   54
 20  \w    135.00 173.00   0.50   10.21    --  110.65  19.00 150.00   76
 21  \w     43.00 102.00   0.50   10.21    --  110.65 -99.00   0.00  118
 22  \w     40.00  65.00   0.50   10.21    --  110.65 -57.00 -60.00   50
 23  \w     40.00  65.00   0.50   10.21    --  110.65 -57.00 -30.00   50
 24  \w     39.00  66.00   0.50   10.21    --  110.65 -57.00 150.00   54
 25  \w    108.00 169.00   0.50   10.21    --  110.65  38.00-180.00  122
 26  \w     39.00  66.00   0.50   10.21    --  110.65 -57.00-150.00   54
 27  \w     39.00  66.00   0.50   10.21    --  110.65 -57.00 120.00   54
 28  \w     40.00  65.00   0.50   10.21    --  110.65 -57.00 -90.00   50
;
_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      0.0354833000
_diffrn_orient_matrix_UB_12      -0.1166423000
_diffrn_orient_matrix_UB_13      0.0393240000
_diffrn_orient_matrix_UB_21      -0.0573177000
_diffrn_orient_matrix_UB_22      -0.0260163000
_diffrn_orient_matrix_UB_23      0.0217635000
_diffrn_orient_matrix_UB_31      -0.0350113000
_diffrn_orient_matrix_UB_32      -0.0755002000
_diffrn_orient_matrix_UB_33      -0.0681757000
_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  0.0303
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            45261
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.000
_diffrn_reflns_theta_min         2.178
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.658
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90968
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.89a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       prism
_exptl_crystal_F_000             1768
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether at --35?'
_exptl_crystal_size_max          0.067
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.518
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.041
_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     519
_refine_ls_number_reflns         9299
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0344
_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^)+(0.0411P)^2^+2.1183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8369
_reflns_number_total             9299
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01683a3.cif
_cod_data_source_block           sh_oph(o-ome)2
_cod_depositor_comments
'Adding full bibliography for 1576939--1576943.cif.'
_cod_database_code               1576941
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C48 H57 N2 O4 Si2 V'
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.842
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(Si2)
2.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C19(H19), C13(H13), C14(H14), C22(H22), C21(H21), C42(H42), C7(H7),
 C41(H41), C40(H40), C9(H9), C48(H48), C32(H32), C39(H39), C8(H8), C38(H38),
 C44(H44), C36(H36), C45(H45), C46(H46), C33(H33), C47(H47), C35(H35), C34(H34)
2.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C28(H28A,H28B,H28C), C12(H12A,H12B,H12C), C30(H30A,H30B,
 H30C), C29(H29A,H29B,H29C), C4(H4A,H4B,H4C), C24(H24A,H24B,H24C), C2(H2A,H2B,
 H2C), C26(H26A,H26B,H26C), C3(H3A,H3B,H3C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              30080
_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 1.291
_oxdiff_exptl_absorpt_empirical_full_min 0.856