Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene.
Maji, Milan; Zeng, Landley; Schrock, Richard R.; Conley, Matthew P.; Carta, Veronica; Chemical science 17 (2026) 421–429; doi:10.1039/d5sc07302b

data_1576723
_publ_section_title
;
 Formation of tungsten ethylidene complexes from diethyl complexes through
 a proton-catalyzed rearrangement of ethylene.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              421
_journal_page_last               429
_journal_paper_doi               10.1039/d5sc07302b
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C23 H23 F18 N O2 W'
_chemical_formula_sum            'C23 H23 F18 N O2 W'
_chemical_formula_weight         871.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-01-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-01-24 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.648(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.517(2)
_cell_length_b                   11.7363(13)
_cell_length_c                   11.8494(11)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      70.13
_cell_measurement_theta_min      5.41
_cell_volume                     2834.1(5)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 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)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            25024
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.040
_diffrn_reflns_theta_min         5.403
_diffrn_source_current           1.1
_diffrn_source_power             0.055
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.910
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6026
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1522 before and 0.0698 after correction.
The Ratio of minimum to maximum transmission is 0.7999.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.042
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_preparation       synthesized
_exptl_crystal_recrystallization_method
'slow cooling of diethyl ether solution to -30 C'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.773
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.49(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         5212
_refine_ls_number_restraints     616
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0215
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0136P)^2^+13.7090P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0510
_refine_ls_wR_factor_ref         0.0514
_reflns_Friedel_coverage         0.859
_reflns_Friedel_fraction_full    0.960
_reflns_Friedel_fraction_max     0.942
_reflns_number_gt                5105
_reflns_number_total             5212
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07302b1.cif
_cod_data_source_block           cu_rrs256mm_0m_b
_cod_database_code               1576723
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.574
_shelx_estimated_absorpt_t_min   0.536
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.51(2)
 0.49(2)
2. 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
3. Restrained distances
 F9-C19 \\sim F8A-C19A
 with sigma of 0.02
 F2-C16 \\sim F2A-C16
 with sigma of 0.04
 F5-C18 \\sim F4A-C18A
 with sigma of 0.02
 F7-C19 \\sim F7A-C19A
 with sigma of 0.02
 F7-C16 \\sim F7A-C16
 with sigma of 0.04
 F6-C16 \\sim F6A-C16
 with sigma of 0.04
 F7-F8 \\sim F7A-F9A
 with sigma of 0.04
 F9-F7 \\sim F8A-F7A
 with sigma of 0.04
 F3-F1 \\sim F3A-F1A
 with sigma of 0.04
 F2-C17 \\sim F2A-C17A
 with sigma of 0.02
 F9-C16 \\sim F8A-C16
 with sigma of 0.04
 F3-C17 \\sim F3A-C17A
 with sigma of 0.02
 F9-F8 \\sim F8A-F9A
 with sigma of 0.04
 F7-F8 \\sim F7-F9 \\sim F8-F9
 with sigma of 0.02
 F6-C18 \\sim F6A-C18A
 with sigma of 0.02
 C16-C18 \\sim C16-C18A
 with sigma of 0.02
 C16-F4 \\sim C16-F5A
 with sigma of 0.04
 C16-C19 \\sim C16-C19A
 with sigma of 0.02
 C16-C17 \\sim C16-C17A
 with sigma of 0.02
 F8-C19 \\sim F9A-C19A
 with sigma of 0.02
 F4-C18 \\sim F5A-C18A
 with sigma of 0.02
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-F1 \\sim F2A-F1A
 with sigma of 0.04
 F3-C16 \\sim F3A-C16
 with sigma of 0.04
 F1-C17 \\sim F1A-C17A
 with sigma of 0.02
 F6-F4 \\sim F6A-F5A
 with sigma of 0.04
 C16-F8 \\sim C16-F9A
 with sigma of 0.04
 C16-F1 \\sim C16-F1A
 with sigma of 0.04
 F5-F6 \\sim F4A-F6A
 with sigma of 0.04
 F5-C16 \\sim F4A-C16
 with sigma of 0.04
 F5-F4 \\sim F4A-F5A
 with sigma of 0.04
 F1-F2 \\sim F2-F3 \\sim F1-F3
 with sigma of 0.04
 F7A-F8A \\sim F7A-F9A \\sim F8A-F9A
 with sigma of 0.02
 F14-C22 \\sim F14A-C22
 with sigma of 0.02
 F15-C22 \\sim F15A-C22
 with sigma of 0.02
 C22-F13 \\sim C22-F13A
 with sigma of 0.02
 F18-C23 \\sim F18A-C23
 with sigma of 0.02
 F17-C23 \\sim F17A-C23
 with sigma of 0.02
 F16-C23 \\sim F16A-C23
 with sigma of 0.02
 F11-C21 \\sim F11A-C21
 with sigma of 0.02
 C21-F12 \\sim C21-F12A
 with sigma of 0.02
 F10-C21 \\sim F10A-C21
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(F9) = Uanis(F5) = Uanis(F2) = Uanis(F3) = Uanis(F7) = Uanis(F6) =
Uanis(C16) = Uanis(F8) = Uanis(F4) = Uanis(C18) = Uanis(F1) = Uanis(C19) =
Uanis(C17) = Uanis(C18A) = Uanis(F6A) = Uanis(F4A) = Uanis(F5A) = Uanis(F8A) =
Uanis(C19A) = Uanis(F7A) = Uanis(F9A) = Uanis(F2A) = Uanis(C17A) = Uanis(F3A) =
Uanis(F1A)
Uanis(F14) = Uanis(F15) = Uanis(C22) = Uanis(F13) = Uanis(F13A) = Uanis(F14A) =
Uanis(F15A)
Uanis(F16) = Uanis(F16A) = Uanis(F17A) = Uanis(F18) = Uanis(F17) = Uanis(C23) =
Uanis(F18A)
Uanis(F11) = Uanis(F10) = Uanis(C21) = Uanis(F12) = Uanis(F12A) = Uanis(F11A) =
Uanis(F10A)
5. 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
6. Others
 Sof(C18A)=Sof(F6A)=Sof(F4A)=Sof(F5A)=Sof(F8A)=Sof(C19A)=Sof(F7A)=Sof(F9A)=
 Sof(F2A)=Sof(C17A)=Sof(F3A)=Sof(F1A)=1-FVAR(1)
 Sof(F9)=Sof(F5)=Sof(F2)=Sof(F3)=Sof(F7)=Sof(F6)=Sof(F8)=Sof(F4)=Sof(C18)=
 Sof(F1)=Sof(C19)=Sof(C17)=FVAR(1)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(2)
 Sof(F14)=Sof(F15)=Sof(F13)=FVAR(2)
 Sof(F16A)=Sof(F18A)=Sof(F17A)=1-FVAR(3)
 Sof(F18)=Sof(F17)=Sof(F16)=FVAR(3)
 Sof(F12A)=Sof(F11A)=Sof(F10A)=1-FVAR(4)
 Sof(F11)=Sof(F10)=Sof(F12)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C13(H13), C6(H6)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B), C1(H1A,H1B)
7.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C11(H11), C10(H10)
7.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              76014
_olex2_submission_special_instructions 'No special instructions were received'