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_1576726
_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         'C24 H25 F18 N O2 W'
_chemical_formula_sum            'C24 H25 F18 N O2 W'
_chemical_formula_weight         885.30
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-24 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.2840(4)
_cell_length_b                   18.2199(7)
_cell_length_c                   30.9881(12)
_cell_measurement_reflns_used    9306
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      72.104
_cell_measurement_theta_min      5.061
_cell_volume                     5806.3(4)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            130741
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.061
_diffrn_reflns_theta_min         5.060
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    8.710
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4264
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1464 before and 0.0717 after correction.
The Ratio of minimum to maximum transmission is 0.5658.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.025
_exptl_crystal_description       plate
_exptl_crystal_F_000             3424
_exptl_crystal_preparation       Synthesized.
_exptl_crystal_recrystallization_method
'Slow-cooling(-30C) of a solution of sample in n-pentane.'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.753
_refine_diff_density_min         -1.469
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         5498
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0330P)^2^+33.8507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0795
_refine_ls_wR_factor_ref         0.0797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5401
_reflns_number_total             5498
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07302b1.cif
_cod_data_source_block           cu_rrs247mm_b
_cod_database_code               1576726
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.508
_shelx_estimated_absorpt_t_min   0.303
_olex2_refinement_description
;
1. 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
2. Restrained distances
 F4-C20 \\sim F4A-C20A
 with sigma of 0.02
 F7-C19 \\sim F7A-C19A
 with sigma of 0.02
 F3-C18 \\sim F3A-C18A
 with sigma of 0.02
 F5-C20 \\sim F5A-C20A
 with sigma of 0.02
 F8-C19 \\sim F8A-C19A
 with sigma of 0.02
 F2-C18 \\sim F2A-C18A
 with sigma of 0.02
 F6-C20 \\sim F6A-C20A
 with sigma of 0.02
 F1-C18 \\sim F1A-C18A
 with sigma of 0.02
 F9-C19 \\sim F9A-C19A
 with sigma of 0.02
 C17-C20 \\sim C17-C20A
 with sigma of 0.02
 C17-C18 \\sim C17-C18A
 with sigma of 0.02
 C17-C19 \\sim C17-C19A
 with sigma of 0.02
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F4-C17 \\sim F4A-C17
 with sigma of 0.04
 F7-F8 \\sim F7A-F8A
 with sigma of 0.04
 F7-F9 \\sim F7A-F9A
 with sigma of 0.04
 F7-C17 \\sim F7A-C17
 with sigma of 0.04
 F3-F2 \\sim F3A-F2A
 with sigma of 0.04
 F3-F1 \\sim F3A-F1A
 with sigma of 0.04
 F3-C17 \\sim F3A-C17
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F5-C17 \\sim F5A-C17
 with sigma of 0.04
 F8-F9 \\sim F8A-F9A
 with sigma of 0.04
 F8-C17 \\sim F8A-C17
 with sigma of 0.04
 F2-F1 \\sim F2A-F1A
 with sigma of 0.04
 F2-C17 \\sim F2A-C17
 with sigma of 0.04
 F6-C17 \\sim F6A-C17
 with sigma of 0.04
 F1-C17 \\sim F1A-C17
 with sigma of 0.04
 F9-C17 \\sim F9A-C17
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(F7) = Uanis(F8) = Uanis(F6) = Uanis(F9) = Uanis(C19) = Uanis(F7A) =
Uanis(F8A) = Uanis(C19A) = Uanis(F9A)
Uanis(F6) = Uanis(C20) = Uanis(F5A) = Uanis(C20A) = Uanis(F6A) = Uanis(F5) =
Uanis(F4A) = Uanis(F4)
Uanis(F3) = Uanis(F2) = Uanis(F1) = Uanis(C18) = Uanis(F3A) = Uanis(F1A) =
Uanis(F2A) = Uanis(C18A)
4. Others
 Sof(F5A)=Sof(C20A)=Sof(F6A)=Sof(F4A)=Sof(F7A)=Sof(F8A)=Sof(C19A)=Sof(F9A)=
 Sof(C18A)=Sof(F3A)=Sof(F1A)=Sof(F2A)=1-FVAR(1)
 Sof(F4)=Sof(F7)=Sof(F3)=Sof(F5)=Sof(F8)=Sof(F2)=Sof(F6)=Sof(F1)=Sof(F9)=
 Sof(C20)=Sof(C18)=Sof(C19)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C13(H13A,H13B), C15(H15A,H15B), C14(H14A,H14B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C5(H5), C6(H6)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C3(H3A,H3B,H3C), C12(H12A,H12B,H12C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              46428
_olex2_submission_special_instructions 'No special instructions were received'