Tungsten-catalyzed stereodivergent isomerization of terminal olefins.
Jankins, Tanner C.; Rubel, Camille Z.; Ho, Hang Chi; Martin-Montero, Raul; Engle, Keary M.; Chemical science 16 (2025) 2307–2315; doi:10.1039/d4sc07093c

data_1573416
_publ_section_title
;
 Tungsten-catalyzed stereodivergent isomerization of terminal olefins.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              2307
_journal_page_last               2315
_journal_paper_doi               10.1039/d4sc07093c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'2(W), 4(C O), 2(C11 H12 N O), 2(C2 H3 O2), 2(C4 H8 O)'
_chemical_formula_sum            'C38 H46 N2 O12 W2'
_chemical_formula_weight         1090.47
_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             2022-02-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-12-07 deposited with the CCDC.	2024-12-03 downloaded from the CCDC.
;
_cell_angle_alpha                66.560(2)
_cell_angle_beta                 71.070(2)
_cell_angle_gamma                71.049(2)
_cell_formula_units_Z            1
_cell_length_a                   8.9455(7)
_cell_length_b                   10.6935(7)
_cell_length_c                   12.0535(8)
_cell_measurement_reflns_used    4400
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.736
_cell_measurement_theta_min      2.471
_cell_volume                     974.88(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0834
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_number            3992
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.406
_diffrn_reflns_theta_min         2.131
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_type              'Bruker TXS'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    5.959
_exptl_absorpt_correction_T_max  0.490
_exptl_absorpt_correction_T_min  0.352
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 44892 reflections, Rint = 0.1158
 (20992 with I > 3sig(I), Rint = 0.0834)
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.857
_exptl_crystal_description       plank
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.015
_refine_diff_density_max         1.988
_refine_diff_density_min         -1.639
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         3992
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0546P)^2^+2.0691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3397
_reflns_number_total             3992
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07093c2.cif
_cod_data_source_block           p-1
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1573415--1573416.cif.
;
_cod_database_code               1573416
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.797
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4T-C3T \\sim C4S-C3S \\sim C3T-C2T \\sim C3S-C2S \\sim C2T-C1T \\sim C2S-C1S
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O1S, C1S, C2S, C3S, C4S, C4T, O1T, C1T, C2T, C3T
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Same fragment restrains
{O1S, C1S, C2S, C3S, C4S} sigma for 1-2: 0.005, 1-3: 0.01
as in
{O1T, C1T, C2T, C3T, C4T}
5. Others
 Sof(O1T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(C3T)=
 Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=1-FVAR(1)
 Sof(O1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=
 Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB),
 C1T(H1TA,H1TB), C2T(H2TA,H2TB), C3T(H3TA,H3TB), C4T(H4TA,H4TB)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11)
6.c X=CH2 refined with riding coordinates:
 C1(H1A,H1B)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              27257
_shelx_hkl_checksum              93596
_olex2_submission_special_instructions 'No special instructions were received'