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_4132789
_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         'C21 H22 F12 N2 O3 W'
_chemical_formula_sum            'C21 H22 F12 N2 O3 W'
_chemical_formula_weight         762.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-06-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.5026(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.16344(15)
_cell_length_b                   15.7018(3)
_cell_length_c                   17.4999(3)
_cell_measurement_reflns_used    15482
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.8184
_cell_measurement_theta_min      2.8401
_cell_volume                     2506.33(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 16.0839
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -49.00   48.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7096   77.0000 -120.0000 97

  2 omega  -49.00   48.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7096   77.0000  120.0000 97

  3 omega   -7.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784   77.0000    0.0000 97

  4 omega   -7.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784   77.0000  120.0000 97

  5 omega  -95.00  -34.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7096 -179.0000 -150.0000 61

  6 omega  -95.00  -34.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7096 -179.0000   90.0000 61

  7 omega  -25.00   20.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7096  -99.0000  150.0000 45

  8 omega  -25.00   62.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784  -99.0000   60.0000 87

  9 omega    3.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784   57.0000  -90.0000 87

 10 omega  -47.00   40.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784  -57.0000    0.0000 87

 11 omega  -25.00   42.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       21.1784  -99.0000  -90.0000 67
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0152287000
_diffrn_orient_matrix_UB_12      -0.0187984000
_diffrn_orient_matrix_UB_13      -0.0367934000
_diffrn_orient_matrix_UB_21      0.0209118000
_diffrn_orient_matrix_UB_22      0.0382901000
_diffrn_orient_matrix_UB_23      -0.0174342000
_diffrn_orient_matrix_UB_31      0.0732934000
_diffrn_orient_matrix_UB_32      -0.0148650000
_diffrn_orient_matrix_UB_33      0.0014786000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0620
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            49281
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.279
_diffrn_reflns_theta_min         2.846
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.726
_exptl_absorpt_correction_T_max  0.861
_exptl_absorpt_correction_T_min  0.711
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.020
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_recrystallization_method
'crystallized from a saturated solution in pentane at -40 degrees Celsius'
_exptl_crystal_size_max          0.4036
_exptl_crystal_size_mid          0.3301
_exptl_crystal_size_min          0.1644
_refine_diff_density_max         0.880
_refine_diff_density_min         -0.783
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         6215
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0300
_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^)+(0.0173P)^2^+2.5371P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0554
_refine_ls_wR_factor_ref         0.0589
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5187
_reflns_number_total             6215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06603_si_007.cif
_cod_data_source_block           kc472
_cod_original_cell_volume        2506.32(7)
_cod_database_code               4132789
_chemical_oxdiff_formula         W1O2F12C30N2
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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 angles
 C2-C2A-C3A
 fixed at 124 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C3A) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.0005 and
sigma for terminal atoms of 0.0005
Uanis(C2) = Uanis(C2A) = Uanis(C3A)
Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C1A) = Uanis(C2A) = Uanis(C3A)
4. Others
 Sof(C2)=Sof(H2b)=Sof(H2a)=Sof(C2A)=Sof(H2Aa)=Sof(C3A)=Sof(H3Aa)=Sof(H3Ab)=
 Sof(H3Ac)=1-FVAR(1)
 Sof(C1)=Sof(H1b)=Sof(H1a)=Sof(C3)=Sof(H3a)=Sof(H3b)=Sof(H3c)=Sof(C1A)=
 Sof(H1Aa)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1A(H1Aa), C2A(H2Aa)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1b,H1a), C2(H2b,H2a)
5.c Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00L(H00L), C00S(H00S), C00T(H00T), C00V(H00V), C00W(H00W),
 C00X(H00X), C00Z(H00Z), C011(H011), C012(H012)
5.d Idealised Me refined as rotating group:
 C00P(H00a,H00b,H00c), C010(H01a,H01b,H01c), C3(H3a,H3b,H3c), C3A(H3Aa,H3Ab,
 H3Ac)
;
_shelx_res_checksum              85424
_shelx_hkl_checksum              98569
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'