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_4132792
_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         'C39 H69 N3 O9 Si2 W'
_chemical_formula_sum            'C39 H69 N3 O9 Si2 W'
_chemical_formula_weight         964.00
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.9297(10)
_cell_length_b                   28.0370(14)
_cell_length_c                   16.5710(9)
_cell_measurement_reflns_used    9898
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.04
_cell_measurement_theta_min      2.41
_cell_volume                     9259.4(8)
_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_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1287
_diffrn_reflns_av_unetI/netI     0.0735
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            72144
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.115
_diffrn_reflns_theta_max         25.115
_diffrn_reflns_theta_min         2.407
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.597
_exptl_absorpt_correction_T_max  0.8620
_exptl_absorpt_correction_T_min  0.6204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0963 before and 0.0699 after correction. The Ratio of minimum to maximum transmission is 0.7197. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       block
_exptl_crystal_F_000             3984
_exptl_crystal_recrystallization_method
'crystallized from a saturated solution in pentane at -40 degrees Celsius'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.891
_refine_diff_density_min         -1.120
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     505
_refine_ls_number_reflns         8153
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0945
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0281P)^2^+10.1270P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0831
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5143
_reflns_number_total             8153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06603_si_004.cif
_cod_data_source_block           fa
_cod_database_code               4132792
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.746
_shelx_estimated_absorpt_t_min   0.652
_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.a Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00H(H00H), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L),
 C00N(H00N), C00P(H00P), C00R(H00R), C00U(H00U), C00W(H00W), C00Y(H00Y),
 C00Z(H00Z), C014(H014), C01A(H01V)
2.b Idealised Me refined as rotating group:
 C00Q(H00A,H00B,H00C), C00T(H00D,H00E,H00F), C00V(H00M,H00O,H00Q), C010(H01A,
 H01B,H01C), C011(H01D,H01E,H01F), C012(H01G,H01H,H01I), C013(H01J,H01K,H01L),
 C016(H01M,H01N,H01O), C017(H01P,H01Q,H01R), C018(H01S,H01T,H01U), C01B(H01W,
 H01X,H01Y), C01C(H01Z,H,HA), C01D(H01,HB,HC), C01E(H0AA,HD,HE), C01F(H1AA,HF,
 HG), C01G(H2AA,HH,HI), C01H(H3AA,HJ,HK), C01I(H4AA,HL,HM)
;
_olex2_submission_special_instructions 'No special instructions were received'