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_1576943
_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         'C47 H55 N2 O3 Si2 V'
_chemical_formula_sum            'C47 H55 N2 O3 Si2 V'
_chemical_formula_weight         803.05
_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             2025-10-30
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-30 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 142.997(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.1091(10)
_cell_length_b                   10.5060(2)
_cell_length_c                   36.0901(17)
_cell_measurement_reflns_used    16820
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.2310
_cell_measurement_theta_min      3.4640
_cell_volume                     4817.1(12)
_computing_cell_refinement       'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.122a 64-bit (release 14-09-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.120a (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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -79.00  22.00   0.50   10.92    --  -50.46  94.00  29.00  202
  2  \w    -13.00  79.00   0.50   10.92    --   50.46 -94.00 -81.00  184
  3  \w   -161.00 -83.00   0.50   43.69    --  -90.00 -94.00 -81.00  156
  4  \w    -80.00 -18.00   0.50   43.69    --  -90.00  94.00  29.00  124
  5  \w     39.00 105.00   0.50   43.69    --  110.67 -94.00 -81.00  132
  6  \w    105.00 178.00   0.50   43.69    --  110.67  94.00  29.00  146
  7  \w   -122.00 -41.00   0.50   10.92    --  -50.46 -45.00 -82.98  162
  8  \w   -122.00 -94.00   0.50   10.92    --  -50.46-125.00  90.00   56
  9  \w   -122.00 -41.00   0.50   10.92    --  -50.46 -46.00-117.90  162
 10  \w   -122.00 -94.00   0.50   10.92    --  -50.46-125.00   0.00   56
 11  \w    -22.00  26.00   0.50   10.92    --   50.46 -19.00-120.00   96
 12  \w   -161.00-103.00   0.50   43.69    --  -90.00 -57.00 -60.00  116
 13  \w   -161.00-100.00   0.50   43.69    --  -90.00 -51.00 -43.66  122
 14  \w    -60.00 -35.00   0.50   43.69    --  -90.00  57.00  30.00   50
 15  \w   -137.00-112.00   0.50   43.69    --  -90.00 -77.00-180.00   50
 16  \w   -120.00 -95.00   0.50   43.69    --  -90.00 -51.00 -43.66   50
 17  \w   -161.00-106.00   0.50   43.69    --  -90.00 -57.00  30.00  110
 18  \w   -118.00 -92.00   0.50   43.69    --  -90.00 -48.00 -55.82   52
 19  \w   -161.00-135.00   0.50   43.69    --  -90.00 -48.00 -55.82   52
 20  \w     39.00  64.00   0.50   43.69    --  110.67 -57.00  60.00   50
 21  \w     41.00  66.00   0.50   43.69    --  110.67 -57.00 -60.00   50
 22  \w     39.00  66.00   0.50   43.69    --  110.67 -57.00 120.00   54
 23  \w     52.00  95.00   0.50   43.69    --  110.67 -77.00 -30.00   86
 24  \w     40.00  66.00   0.50   43.69    --  110.67 -57.00 -90.00   52
 25  \w     39.00  65.00   0.50   43.69    --  110.67 -57.00 -30.00   52
 26  \w    110.00 172.00   0.50   43.69    --  110.67  77.00 150.00  124
 27  \w     41.00 101.00   0.50   43.69    --  110.67 -99.00-180.00  120
;
_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      0.0383055000
_diffrn_orient_matrix_UB_12      0.1226159000
_diffrn_orient_matrix_UB_13      0.0370743000
_diffrn_orient_matrix_UB_21      -0.0247740000
_diffrn_orient_matrix_UB_22      -0.0589599000
_diffrn_orient_matrix_UB_23      0.0265158000
_diffrn_orient_matrix_UB_31      0.1123161000
_diffrn_orient_matrix_UB_32      -0.0547918000
_diffrn_orient_matrix_UB_33      0.0543487000
_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  0.0430
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            45063
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        65.994
_diffrn_reflns_theta_max         65.994
_diffrn_reflns_theta_min         3.479
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.488
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87055
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.120a (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    1.107
_exptl_crystal_description       plate
_exptl_crystal_F_000             1704
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether:pentane at --35?'
_exptl_crystal_size_max          0.129
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.356
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         8382
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0563P)^2^+1.2308P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6723
_reflns_number_total             8382
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc01683a3.cif
_cod_data_source_block           sh-alkylidyne-4
_cod_depositor_comments
'Adding full bibliography for 1576939--1576943.cif.'
_cod_original_cell_volume        4817.1(8)
_cod_database_code               1576943
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C47 H55 N2 O3 Si2 V'
_cell_oxdiff_angle_alpha         90.0277(13)
_cell_oxdiff_angle_beta          143.001(3)
_cell_oxdiff_angle_gamma         89.9847(14)
_cell_oxdiff_length_a            21.1168(5)
_cell_oxdiff_length_b            10.50334(14)
_cell_oxdiff_length_c            36.0897(7)
_cell_oxdiff_measurement_reflns_used 16834
_cell_oxdiff_volume              4817.17(15)
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.740
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name SH-alkylidyne-4.par
_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. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(Si2)
3.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C14(H14), C13(H13), C11(H11), C6(H6), C37(H37), C5(H5), C41(H41),
 C28(H28), C31(H31), C25(H25), C43(H43), C35(H35), C33(H33), C47(H47), C32(H32),
  C34(H34), C40(H40), C26(H26), C27(H27), C38(H38), C39(H39), C44(H44),
 C45(H45), C46(H46)
3.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C22(H22A,H22B,H22C), C2(H2A,H2B,H2C), C21(H21A,H21B,H21C),
 C29(H29A,H29B,H29C), C4(H4A,H4B,H4C), C20(H20A,H20B,H20C), C18(H18A,H18B,H18C),
  C17(H17A,H17B,H17C), C16(H16A,H16B,H16C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63793
_shelx_fab_checksum              48103
_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 1.326
_oxdiff_exptl_absorpt_empirical_full_min 0.847