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_4132790
_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 H21 F12 N3 O3 W'
_chemical_formula_sum            'C23 H21 F12 N3 O3 W'
_chemical_formula_weight         799.28
_chemical_name_systematic        WO(OR)2(py)3
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.62240(10)
_cell_length_b                   15.53380(10)
_cell_length_c                   24.4917(3)
_cell_measurement_reflns_used    17773
_cell_measurement_temperature    100(4)
_cell_measurement_theta_max      30.6810
_cell_measurement_theta_min      2.8741
_cell_volume                     5559.26(9)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(4)
_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  -98.00  -47.00   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.7904 -179.0000 -120.0000 102

  2 omega  -25.00   20.00   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.7904  -99.0000  120.0000 90

  3 omega   34.00   98.00   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  179.0000  150.0000 128

  4 omega    1.00   91.00   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   57.0000  -90.0000 180

  5 omega  -11.00   85.00   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   19.0000 -150.0000 192

  6 omega  -50.00   15.50   0.5000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  -38.0000  150.0000 131
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0138505000
_diffrn_orient_matrix_UB_12      0.0417813000
_diffrn_orient_matrix_UB_13      0.0079437000
_diffrn_orient_matrix_UB_21      0.0104794000
_diffrn_orient_matrix_UB_22      -0.0104632000
_diffrn_orient_matrix_UB_23      0.0277139000
_diffrn_orient_matrix_UB_31      0.0453433000
_diffrn_orient_matrix_UB_32      0.0151918000
_diffrn_orient_matrix_UB_33      -0.0028061000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0492
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            48961
_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         28.282
_diffrn_reflns_theta_min         2.970
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.267
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.998
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
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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            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.910
_exptl_crystal_description       block
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.2269
_exptl_crystal_size_mid          0.1714
_exptl_crystal_size_min          0.0587
_refine_diff_density_max         1.672
_refine_diff_density_min         -1.570
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         13786
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0335
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0315P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0677
_refine_ls_wR_factor_ref         0.0725
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11406
_reflns_number_total             13786
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06603_si_003.cif
_cod_data_source_block           kc323-3
_cod_database_code               4132790
_chemical_oxdiff_formula         W1O3N3F12C30H50
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H013(0.025) H31(0.025) H30(0.024) H016(0.027) H017(0.028)
 H018(0.027) H019(0.04) H01B(0.029) H01D(0.033) H01F(0.026) H01G(0.027)
 H01J(0.036) H01K(0.032) H01H(0.059) H01I(0.059) H01L(0.059) H01M(0.028)
 H01A(0.041) H01C(0.041) H01E(0.041) H01O(0.029) H01R(0.03) H01S(0.036)
 H01T(0.032) H01V(0.047) H01W(0.034) H01X(0.037) H01Z(0.035) H02A(0.062)
 H02B(0.062) H02C(0.062) H022(0.035) H023(0.035) H02G(0.054) H02H(0.054)
 H02I(0.054) H026(0.043) H028(0.048) H029(0.04) H02D(0.043) H02E(0.064)
 H02F(0.061)
 Fixed X: H013(-0.0865) H31(-0.1047) H30(0.1406) H016(0.1313) H017(0.5801)
 H018(-0.1611) H019(0.448) H01B(0.3548) H01D(0.5764) H01F(0.3974) H01G(0.0697)
 H01J(0.6858) H01K(0.4596) H01H(0.1331) H01I(0.226) H01L(0.2188) H01M(0.6444)
 H01A(0.372) H01C(0.3304) H01E(0.4387) H01O(0.0877) H01R(-0.065) H01S(-0.1362)
 H01T(0.6068) H01V(0.5278) H01W(0.0847) H01X(0.6248) H01Z(0.1313) H02A(0.6478)
 H02B(0.7441) H02C(0.7261) H022(0.7002) H023(0.2004) H02G(-0.0917) H02H(-0.109)
 H02I(-0.0094) H026(0.2344) H028(0.2695) H029(-0.05) H02D(0.7352) H02E(0.4335)
 H02F(0.3917)
 Fixed Y: H013(0.3089) H31(0.1805) H30(0.2599) H016(0.386) H017(0.507)
 H018(0.1995) H019(0.2353) H01B(0.3347) H01D(0.1336) H01F(0.3445) H01G(0.0524)
 H01J(0.4162) H01K(0.2871) H01H(0.3659) H01I(0.3513) H01L(0.321) H01M(0.2561)
 H01A(0.3544) H01C(0.4497) H01E(0.436) H01O(0.2838) H01R(0.2523) H01S(0.45)
 H01T(0.2462) H01V(-0.0024) H01W(0.5272) H01X(0.646) H01Z(-0.0818) H02A(0.1983)
 H02B(0.2296) H02C(0.2318) H022(0.6708) H023(0.0623) H02G(0.1328) H02H(0.0314)
 H02I(0.0704) H026(-0.1438) H028(-0.0691) H029(0.562) H02D(0.5523) H02E(-
 0.0202) H02F(0.1016)
 Fixed Z: H013(0.5986) H31(0.7156) H30(0.7676) H016(0.6866) H017(0.3699)
 H018(0.8014) H019(0.4083) H01B(0.1524) H01D(0.2851) H01F(0.2431) H01G(0.7366)
 H01J(0.2363) H01K(0.0882) H01H(0.5564) H01I(0.5252) H01L(0.5874) H01M(0.2129)
 H01A(0.4334) H01C(0.4333) H01E(0.4321) H01O(0.8539) H01R(0.873) H01S(0.5897)
 H01T(0.1218) H01V(0.3081) H01W(0.6791) H01X(0.3472) H01Z(0.7575) H02A(0.4424)
 H02B(0.4685) H02C(0.4037) H022(0.2665) H023(0.5993) H02G(0.5217) H02H(0.5271)
 H02I(0.5406) H026(0.6971) H028(0.6182) H029(0.6296) H02D(0.2116) H02E(0.3825)
 H02F(0.4321)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-03-15
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'