Initiating olefin metathesis: alkylidenes from molecular Mo(iv)-oxo species, olefins and base-promoted proton transfer
Nater, Darryl F.; de Zwart, Felix J.; Kaeffer, Nicolas; Copéret, Christophe; Chemical Science  (2025) –; doi:10.1039/D5SC06662J

data_1576235
_publ_section_title
;
 Initiating olefin metathesis: alkylidenes from molecular Mo(iv)-oxo
 species, olefins and base-promoted proton transfer
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC06662J
_journal_year                    2025
_chemical_formula_moiety         'C22.692 H17.823 F15.189 Mo N3 O3 Si0.314'
_chemical_formula_sum            'C22.69 H17.82 F15.19 Mo N3 O3 Si0.31'
_chemical_formula_weight         773.90
_chemical_name_systematic        MoO(OtBuF9)2(py)3
_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     direct
_audit_creation_date             2021-10-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-10-25 deposited with the CCDC.	2025-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                89.2540(10)
_cell_angle_beta                 75.6330(10)
_cell_angle_gamma                78.1320(10)
_cell_formula_units_Z            2
_cell_length_a                   9.7717(2)
_cell_length_b                   9.82510(10)
_cell_length_c                   15.0404(2)
_cell_measurement_reflns_used    37807
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.9750
_cell_measurement_theta_min      2.0920
_cell_volume                     1367.84(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.928
_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    -60.85 144.65   0.50   10.00    --  -22.10  73.75-130.74  411
  2  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75  25.26  411
  3  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75 127.26  411
  4  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75 -79.74  411
  5  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75 -25.74  411
  6  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75  76.26  411
  7  \w    -60.85 144.65   0.50   10.00    --  -22.10  73.75 178.26  411
  8  \w    -46.85 160.65   0.50   10.00    --   -7.10  73.75 -25.74  415
  9  \f    -25.74 334.26   0.50   10.00 146.15 -22.10  73.75    --   720
 10  \f    -25.74 334.26   0.50   10.00 -61.84 -22.10  73.75    --   720
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0517
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52515
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.027
_diffrn_reflns_theta_min         2.120
_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86230
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark black'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.879
_exptl_crystal_description       plate
_exptl_crystal_F_000             764
_exptl_crystal_preparation       'reduction of dioxo compound'
_exptl_crystal_recrystallization_method pentane
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.794
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     666
_refine_ls_number_reflns         6778
_refine_ls_number_restraints     607
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0493P)^2^+2.1430P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1041
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5951
_reflns_number_total             6778
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06662j2.cif
_cod_data_source_block           dn_290
_cod_database_code               1576235
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.834
_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. Shared sites
{C20, C20A, Si20}
3. Restrained distances
 F13-C22 \\sim F15-C22 \\sim F14-C22
 with sigma of 0.01
 F6-C18 \\sim F4-C18 \\sim F5-C18 \\sim F9-C19 \\sim F7-C19 \\sim F8-C19 \\sim
F2-C17 \\sim F3-C17 \\sim F1-C17
 with sigma of 0.01
 F9A-F8A \\sim F8A-F7A \\sim F9A-F7A \\sim F6A-F5A \\sim F5A-F4A \\sim F6A-F4A
\\sim F2A-F1A \\sim F3A-F2A
 \\sim F3A-F1A
 with sigma of 0.01
 C17-C16 \\sim C18-C16 \\sim C19-C16
 with sigma of 0.01
 C21A-C20 \\sim C23A-C20 \\sim C22A-C20
 with sigma of 0.01
 F3-F1 \\sim F2-F1 \\sim F3-F2 \\sim F6-F5 \\sim F5-F4 \\sim F6-F4 \\sim F9-F8
\\sim F8-F7 \\sim F9-F7
 with sigma of 0.01
 F11-C21 \\sim F10-C21 \\sim F12-C21
 with sigma of 0.01
 C26-C25 \\sim C25-C24 \\sim C26-C24
 with sigma of 0.01
 F18-C23 \\sim F17-C23 \\sim F16-C23
 with sigma of 0.01
 F17A-F16A \\sim F18A-F17A \\sim F18A-F16A \\sim F12A-F11A \\sim F12A-F10A
\\sim F11A-F10A \\sim F15A-
 F13A \\sim F14A-F13A \\sim F15A-F14A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C20) = Uanis(C20A) = Uanis(Si20)
Uiso(C26) = Uiso(C24) = Uiso(C25)
5. Rigid body (RIGU) restrains
 F10, F11, F12, F13, F14, F15, F16, F17, F18, O3, C20, C21, C22, C23, C21A,
 F10A, F12A, F11A, C22A, F14A, F15A, F13A, F18A, F16A, F17A, C23A, C20A, Si20,
 C25, C26, C24
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F1, F2, F3, F4, F5, F6, F7, F8, F9, O2, C16, C17, C18, C19, F1A, F2A, F3A,
 F4A, F5A, F6A, F7A, F8A, F9A, C17A, C18A, C19A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 1*[Sof(F10)+Sof(F11)+Sof(F12)+Sof(F13)+Sof(F14)+Sof(F15)+Sof(F16)+Sof(F17)+
 Sof(F18)+Sof(C20)+Sof(C21)+Sof(C22)+Sof(C23)]+1*[Sof(C21A)+Sof(F10A)+Sof(F12A)+
 Sof(F11A)+Sof(C22A)+Sof(F14A)+Sof(F15A)+Sof(F13A)+Sof(F18A)+Sof(F16A)+
 Sof(F17A)+Sof(C23A)+Sof(C20A)]+1*[Sof(Si20)+Sof(C25)+Sof(H25A)+Sof(H25B)+
 Sof(H25C)+Sof(C26)+Sof(H26A)+Sof(H26B)+Sof(H26C)+Sof(C24)+Sof(H24A)+Sof(H24B)+
 Sof(H24C)]=1 with esd of 0.001
 Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=
 Sof(F18)=Sof(C20)=Sof(C21)=Sof(C22)=Sof(C23)=FVAR(1)
 Sof(C21A)=Sof(F10A)=Sof(F12A)=Sof(F11A)=Sof(C22A)=Sof(F14A)=Sof(F15A)=
 Sof(F13A)=Sof(F18A)=Sof(F16A)=Sof(F17A)=Sof(C23A)=Sof(C20A)=FVAR(2)
 Sof(Si20)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(3)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=
 Sof(F9A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(C17)=Sof(C18)=Sof(C19)=FVAR(4)
7.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15)
7.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              54646
_olex2_exptl_crystal_mounting_method 'paratone oil'
_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
;