C-H Activation and Proton Transfer Initiate Alkene Metathesis Activity of the Tungsten(IV)-Oxo Complex.
Chan, Ka Wing; Lam, Erwin; D'Anna, Vincenza; Allouche, Florian; Michel, Carine; Safonova, Olga V.; Sautet, Philippe; Copéret, Christophe; Journal of the American Chemical Society 140 (2018) 11395–11401; doi:10.1021/jacs.8b06603

data_4132794
_publ_section_title
;
 C-H Activation and Proton Transfer Initiate Alkene Metathesis Activity of
 the Tungsten(IV)-Oxo Complex.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11395
_journal_page_last               11401
_journal_paper_doi               10.1021/jacs.8b06603
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C23 H15 F18 N3 O3 W'
_chemical_formula_sum            'C23 H15 F18 N3 O3 W'
_chemical_formula_weight         907.23
_chemical_name_systematic        WO(OtBuF9)2(pyr)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     dual
_audit_creation_date             2017-05-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                89.146(2)
_cell_angle_beta                 75.888(2)
_cell_angle_gamma                78.116(2)
_cell_formula_units_Z            2
_cell_length_a                   9.8228(6)
_cell_length_b                   9.9086(6)
_cell_length_c                   14.9056(8)
_cell_measurement_reflns_used    9536
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.23
_cell_measurement_theta_min      2.49
_cell_volume                     1375.87(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0597
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_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       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            71189
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.307
_diffrn_reflns_theta_min         2.487
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.355
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6433
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0787 before and 0.0633 after correction. The Ratio of minimum to maximum transmission is 0.8627. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.190
_exptl_crystal_description       plate
_exptl_crystal_F_000             868
_exptl_crystal_recrystallization_method
'crystallized from a saturated solution in toluene'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.761
_refine_diff_density_min         -0.831
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     591
_refine_ls_number_reflns         6834
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0205
_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^)+(0.0128P)^2^+1.1579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0385
_refine_ls_wR_factor_ref         0.0400
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6235
_reflns_number_total             6834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06603_si_005.cif
_cod_data_source_block           fa
_cod_database_code               4132794
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F0) = Uanis(F11) = Uanis(C2) = Uanis(C7) = Uanis(F7) = Uanis(F12)
Uanis(C0) = Uanis(C8) = Uanis(F1) = Uanis(F1A) = Uanis(F19) = Uanis(F6)
3. Rigid body (RIGU) restrains
 C6, C1, F1B, F4, F1C, F2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(F2)=Sof(F4)=Sof(F9)=Sof(C0)=Sof(C6)=Sof(C7)=Sof(F11)=Sof(F12)=Sof(F18)=
 Sof(F19)=Sof(F1A)=Sof(F10A)=1-FVAR(1)
 Sof(F0)=Sof(F1)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F10B)=Sof(C1)=Sof(C2)=Sof(C8)=
 Sof(F10)=Sof(F1B)=Sof(F1C)=FVAR(1)
 Sof(F3)=Sof(F5)=Sof(F13B)=Sof(F12B)=Sof(F15B)=Sof(F11B)=Sof(F14B)=Sof(C3)=
 Sof(C5)=Sof(C11)=Sof(F16A)=Sof(F17A)=1-FVAR(2)
 Sof(F17B)=Sof(F16B)=Sof(C4)=Sof(C9)=Sof(C10)=Sof(F15A)=Sof(F14A)=Sof(F13)=
 Sof(F12A)=Sof(F11A)=Sof(F13A)=Sof(F14)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C00P(H00P), C00Q(H00Q), C00S(H00S), C00T(H00T),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011),
 C013(H013), C014(H014), C016(H016)
;
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'