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_4132791
_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         'C29 H59 Cl2 N O9 Si2 W'
_chemical_formula_sum            'C29 H59 Cl2 N O9 Si2 W'
_chemical_formula_weight         876.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-09-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.0652(19)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.45008(18)
_cell_length_b                   14.9417(4)
_cell_length_c                   14.5852(3)
_cell_measurement_reflns_used    8112
_cell_measurement_temperature    111.92(15)
_cell_measurement_theta_max      30.5492
_cell_measurement_theta_min      2.8228
_cell_volume                     2033.71(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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      111.92(15)
_diffrn_detector_area_resol_mean 16.0839
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -92.00    8.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.7904  -77.0000   90.0000 100

  2 omega  -91.00    0.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.7904  -57.0000 -180.0000 91

  3 omega  -23.00   64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  -99.0000   60.0000 87

  4 omega   34.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  179.0000 -120.0000 64

  5 omega  -91.00    0.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.7904  -57.0000  -60.0000 91

  6 omega   34.00   66.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  179.0000    0.0000 32
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0743078000
_diffrn_orient_matrix_UB_12      0.0076407000
_diffrn_orient_matrix_UB_13      0.0008931000
_diffrn_orient_matrix_UB_21      -0.0094943000
_diffrn_orient_matrix_UB_22      -0.0041139000
_diffrn_orient_matrix_UB_23      -0.0490379000
_diffrn_orient_matrix_UB_31      -0.0129944000
_diffrn_orient_matrix_UB_32      0.0466531000
_diffrn_orient_matrix_UB_33      -0.0044779000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17559
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.828
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.074
_exptl_absorpt_correction_T_max  0.795
_exptl_absorpt_correction_T_min  0.607
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.5285
_exptl_crystal_size_mid          0.3008
_exptl_crystal_size_min          0.2052
_refine_diff_density_max         2.901
_refine_diff_density_min         -1.959
_refine_diff_density_rms         0.137
_refine_ls_abs_structure_details
;
 Flack x determined using 3296 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.070(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     350
_refine_ls_number_reflns         8276
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0470P)^2^+12.9670P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1201
_refine_ls_wR_factor_ref         0.1226
_reflns_Friedel_coverage         0.919
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                7813
_reflns_number_total             8276
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06603_si_002.cif
_cod_data_source_block           kc187
_cod_original_cell_volume        2033.72(8)
_cod_database_code               4132791
_chemical_oxdiff_formula         W1Si2O10C40H60N1
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si7-O10 = Si7-O9 = Si7-O5 = Si7-O8 = Si7-O2AA = Si7-O6
 1.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Si7) = Uanis(O10) = Uanis(O8) = Uanis(O2AA) = Uanis(C19) = Uanis(C27) =
Uanis(C1A) = Uanis(C20) = Uanis(C30) = Uanis(C22) = Uanis(C28) = Uanis(O5) =
Uanis(O6) = Uanis(O9) = Uanis(C31) = Uanis(C32B) = Uanis(C32A) = Uanis(C3B) =
Uanis(C4B) = Uanis(C5B) = Uanis(C3A) = Uanis(C4A) = Uanis(C5A)
4. Others
 Sof(O5)=Sof(O6)=Sof(O9)=Sof(C32B)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=
 Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=
 1-FVAR(1)
 Sof(O10)=Sof(O8)=Sof(O2AA)=Sof(C32A)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=
 Sof(C3A)=Sof(H3AB)=Sof(H3AC)=Sof(H3AD)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=
 FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C3AA(H3AA), C2(H2), C2AA(H2AA), C1AA(H1AA)
5.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C0AA(H0AA,H0AB,H0AC), C15(H15A,H15B,H15C), C9(H9A,H9B,H9C),
 C12(H12A,H12B,H12C), C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C11(H11A,H11B,
 H11C), C13(H13A,H13B,H13C), C1A(H1AB,H1AC,H1AD), C20(H20A,H20C,H20B), C30(H30C,
 H30B,H30A), C22(H22A,H22B,H22C), C28(H28C,H28B,H28A), C31(H31A,H31B,H31C),
 C3B(H3BA,H3BB,H3BC), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,H5BC), C3A(H3AB,H3AC,
 H3AD), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-09-07
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'