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_1576727
_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         'C56 H68 F9 N5 O W2, 0.5(C4 H10 O)'
_chemical_formula_sum            'C58 H73 F9 N5 O1.5 W2'
_chemical_formula_weight         1402.91
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-08-15 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                   20.8163(6)
_cell_length_b                   13.7960(4)
_cell_length_c                   39.1164(11)
_cell_measurement_reflns_used    9777
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      70.04
_cell_measurement_theta_min      4.40
_cell_volume                     11233.5(6)
_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      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0780
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 1.000
_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       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            193781
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.178
_diffrn_reflns_theta_min         2.259
_diffrn_source_current           1.1
_diffrn_source_power             0.055
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.095
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6014
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1640 before and 0.0850 after correction.
The Ratio of minimum to maximum transmission is 0.7984.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.659
_exptl_crystal_description       plate
_exptl_crystal_F_000             5576
_exptl_crystal_preparation       synthesized
_exptl_crystal_recrystallization_method 'slow cooling of diethyl ether'
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         3.052
_refine_diff_density_min         -3.561
_refine_diff_density_rms         0.188
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.242(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1210
_refine_ls_number_reflns         21316
_refine_ls_number_restraints     1513
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0165P)^2^+186.8509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1219
_reflns_Friedel_coverage         0.966
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                20091
_reflns_number_total             21316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07302b1.cif
_cod_data_source_block           rrs284mm_a
_cod_original_formula_sum        'C58 H73 F9 N5 O1.50 W2'
_cod_database_code               1576727
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.688
_shelx_estimated_absorpt_t_min   0.470
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.758(18)
 0.242(18)
2. 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
3. Restrained distances
 C61-C62 \\sim C57-C58 \\sim C60-C59 \\sim C64-C63
 with sigma of 0.02
 O2-C58 \\sim O2-C59 \\sim O3-C62 \\sim O3-C63
 with sigma of 0.02
 F4A-C55A \\sim F4B-C55B
 with sigma of 0.02
 F3A-C54A \\sim F3B-C54B
 with sigma of 0.02
 F2A-C54A \\sim F2B-C54B
 with sigma of 0.02
 F2A-C53A \\sim F2B-C53A
 with sigma of 0.04
 F9A-C53A \\sim F9B-C53A
 with sigma of 0.04
 C53A-F6A \\sim C53A-F6B
 with sigma of 0.04
 F1A-C54A \\sim F1B-C54B
 with sigma of 0.02
 F5A-C55A \\sim F5B-C55B
 with sigma of 0.02
 F5A-C53A \\sim F5B-C53A
 with sigma of 0.04
 F9A-F7A \\sim F9B-F7B
 with sigma of 0.04
 C54A-C53A \\sim C54B-C53A
 with sigma of 0.02
 F8A-F7A \\sim F8B-F7B
 with sigma of 0.04
 C56A-F9A \\sim C56B-F9B
 with sigma of 0.02
 C56A-C53A \\sim C56B-C53A
 with sigma of 0.02
 C56A-F8A \\sim C56B-F8B
 with sigma of 0.02
 C56A-F7A \\sim C56B-F7B
 with sigma of 0.02
 F2A-F1A \\sim F2B-F1B
 with sigma of 0.04
 F1A-C53A \\sim F1B-C53A
 with sigma of 0.04
 F5A-F6A \\sim F5B-F6B
 with sigma of 0.04
 C53A-C55A \\sim C53A-C55B
 with sigma of 0.02
 F6A-C55A \\sim F6B-C55B
 with sigma of 0.02
 F9A-F8A \\sim F9B-F8B
 with sigma of 0.04
 C53A-F8A \\sim C53A-F8B
 with sigma of 0.04
 C53A-F7A \\sim C53A-F7B
 with sigma of 0.04
 F3A-F2A \\sim F3B-F2B
 with sigma of 0.04
 F3A-F1A \\sim F3B-F1B
 with sigma of 0.04
 F3A-C53A \\sim F3B-C53A
 with sigma of 0.04
 F4A-F5A \\sim F4B-F5B
 with sigma of 0.04
 F4A-C53A \\sim F4B-C53A
 with sigma of 0.04
 F4A-F6A \\sim F4B-F6B
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(C61) = Uanis(C64) = Uanis(C63) = Uanis(O3) = Uanis(C62) = Uanis(C57) =
Uanis(C58) = Uanis(O2) = Uanis(C59) = Uanis(C60)
Uanis(F5A) = Uanis(F6A) = Uanis(C55A) = Uanis(F4B) = Uanis(F6B) = Uanis(C55B) =
Uanis(F4A) = Uanis(F5B)
Uanis(F3B) = Uanis(F3A) = Uanis(C54B) = Uanis(C54A) = Uanis(F1B) = Uanis(F1A) =
Uanis(F2A) = Uanis(F2B)
Uanis(F4A) = Uanis(F5A) = Uanis(F6A) = Uanis(C55A) = Uanis(F4B) = Uanis(F5B) =
Uanis(F6B) = Uanis(C55B)
Uanis(F8A) = Uanis(F9B) = Uanis(F8B) = Uanis(F9A) = Uanis(F7A) = Uanis(F7B) =
Uanis(C56B) = Uanis(C56A)
Uanis(C20A) = Uanis(C21A) = Uanis(C19A) = Uanis(C22A) = Uanis(C23A)
Uanis(N5) = Uanis(C56) = Uanis(C55) = Uanis(C54) = Uanis(C53) = Uanis(C52)
Uanis(N5A) = Uanis(C48A) = Uanis(C49A) = Uanis(C50A) = Uanis(C51A) = Uanis(C52A)
Uanis(N1) = Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C4) = Uanis(C5) =
Uanis(C6) = Uanis(C8) = Uanis(C7) = Uanis(C9) = Uanis(C11) = Uanis(C10)
Uanis(N3) = Uanis(C28)
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(O3)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(1)
 Sof(O2)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C58)=Sof(H58A)=Sof(H58B)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=
 Sof(F9B)=Sof(C54B)=Sof(C55B)=Sof(C56B)=1-FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=
 Sof(F9A)=Sof(C54A)=Sof(C55A)=Sof(C56A)=FVAR(2)
7.a Riding coordinates:
 C61(H61A,H61B,H61C), C64(H64A,H64B,H64C)
7.b Ternary CH refined with riding coordinates:
 N1A(H1A), C9A(H9A), C21A(H21A), C26A(H26A), C33A(H33A), C38A(H38A),
 C45A(H45A), N1(H1), C9(H9), C21(H21), C30(H30), C37(H37), C42(H42), C49(H49)
7.c Secondary CH2 refined with riding coordinates:
 C15A(H15A,H15B), C15(H15C,H15D), C58(H58A,H58B), C59(H59A,H59B), C62(H62A,
 H62B), C63(H63A,H63B)
7.d Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C6A(H6A), C7A(H7A), C17A(H17A), C18A(H18A), C19A(H19A), C29A(H29A),
 C30A(H30A), C31A(H31A), C41A(H41A), C42A(H42A), C43A(H43A), C48A(H48A),
 C49A(H49A), C50A(H50A), C51A(H51A), C52A(H52A), C5(H5), C6(H6), C7(H7),
 C17(H17), C18(H18), C19(H19), C33(H33), C34(H34), C35(H35), C45(H45), C46(H46),
  C47(H47), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56)
7.e Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C16A(H16A,
 H16B,H16C), C22A(H22A,H22B,H22C), C23A(H23A,H23B,H23C), C27A(H27A,H27B,H27C),
 C28A(H28A,H28B,H28C), C34A(H34A,H34B,H34C), C35A(H35A,H35B,H35C), C39A(H39A,
 H39B,H39C), C40A(H40A,H40B,H40C), C46A(H46A,H46B,H46C), C47A(H47A,H47B,H47C),
 C4(H4A,H4B,H4C), C10(H10D,H10E,H10F), C11(H11D,H11E,H11F), C16(H16D,H16E,H16F),
  C22(H22D,H22E,H22F), C23(H23D,H23E,H23F), C31(H31B,H31C,H31D), C32(H32A,H32B,
 H32C), C38(H38B,H38C,H38D), C39(H39D,H39E,H39F), C43(H43B,H43C,H43D), C44(H44A,
 H44B,H44C), C50(H50B,H50C,H50D), C51(H51B,H51C,H51D), C57(H57A,H57B,H57C),
 C60(H60A,H60B,H60C)
;
_shelx_res_checksum              70052
_olex2_submission_special_instructions 'No special instructions were received'