Magnitude and consequences of OR ligand σ-donation on alkene metathesis activity in d0 silica supported (SiO)W(NAr)(CHtBu)(OR) catalysts
Mougel, V.; Copéret, C.; Chemical Science 5 (2014) 2475–; doi:10.1039/c4sc00230j

data_1514376
_publ_section_title
;
 Magnitude and consequences of OR ligand \s-donation on alkene metathesis
 activity in d0 silica supported (&#xE002;SiO)W(NAr)(&#xE001;CHtBu)(OR)
 catalysts
;
_journal_issue                   6
_journal_name_full               'Chemical Science'
_journal_page_first              2475
_journal_paper_doi               10.1039/c4sc00230j
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C25 H27 F18 N O2 W'
_chemical_formula_sum            'C25 H27 F18 N O2 W'
_chemical_formula_weight         899.32
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-12-13
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4720)
;
_cell_angle_alpha                65.712(3)
_cell_angle_beta                 71.109(3)
_cell_angle_gamma                68.540(3)
_cell_formula_units_Z            6
_cell_length_a                   15.3435(4)
_cell_length_b                   17.6683(5)
_cell_length_c                   21.0020(5)
_cell_measurement_reflns_used    16356
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      30.3180
_cell_measurement_theta_min      3.1450
_cell_volume                     4728.0(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector_area_resol_mean 16.0839
_diffrn_measured_fraction_theta_full 0.9915
_diffrn_measured_fraction_theta_max 0.8618
_diffrn_measurement_details
;
  1 omega  -98.00  -46.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.6342 -179.0000  -90.0000 52

  2 omega  -25.00   20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.6342  -99.0000  150.0000 45

  3 omega   34.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  179.0000 -180.0000 64

  4 omega    1.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   57.0000  -60.0000 89

  5 omega  -13.00   85.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   19.0000 -120.0000 98

  6 omega  -50.00   48.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  -38.0000 -180.0000 98
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0477091000
_diffrn_orient_matrix_UB_12      -0.0021152000
_diffrn_orient_matrix_UB_13      0.0073696000
_diffrn_orient_matrix_UB_21      0.0000006000
_diffrn_orient_matrix_UB_22      0.0177960000
_diffrn_orient_matrix_UB_23      -0.0370513000
_diffrn_orient_matrix_UB_31      0.0172781000
_diffrn_orient_matrix_UB_32      -0.0420827000
_diffrn_orient_matrix_UB_33      -0.0023556000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0826
_diffrn_reflns_av_unetI/netI     0.1616
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            46595
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.765
_diffrn_reflns_theta_min         2.798
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.796
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.895
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2616
_exptl_crystal_size_max          0.2415
_exptl_crystal_size_mid          0.1542
_exptl_crystal_size_min          0.1239
_refine_diff_density_max         2.617
_refine_diff_density_min         -3.906
_refine_diff_density_rms         0.292
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1213
_refine_ls_number_reflns         25449
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      0.990
_refine_ls_R_factor_all          0.0972
_refine_ls_R_factor_gt           0.0521
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0651P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1216
_refine_ls_wR_factor_ref         0.1715
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16542
_reflns_number_total             25449
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc00230j1.cif
_cod_data_source_block           WOtBuF9
_cod_depositor_comments          'Adding full bibliography for 1514376.cif.'
_cod_database_code               1514376
_shelxl_version_number           2012-9
_chemical_oxdiff_formula         'W1 C25 H28 F18 N1 O2'
_reflns_odcompleteness_completeness 99.15
_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. Uiso/Uaniso restraints and constraints
Uanis(F108) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(F107) \\sim Ueq,
Uanis(F106) \\sim Ueq, Uanis(F105) \\sim Ueq, Uanis(C119) \\sim Ueq,
Uanis(F103) \\sim Ueq, Uanis(F104) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C209) = Uanis(C201)
Uanis(C216) = Uanis(F207) = Uanis(C215)
Uanis(F115) = Uanis(C123) = Uanis(C121)
Uanis(O101) = Uanis(C121) = Uanis(C122)
Uanis(C222) = Uanis(F212) = Uanis(C219)
Uanis(C116) = Uanis(C113)
Uanis(C69) = Uanis(C212)
Uanis(F13) = Uanis(C25) = Uanis(C22)
3.a Ternary CH refined with riding coordinates:
 C7(H7), C109(H109), C106(H106), C209(H209), C10(H10), C206(H206)
3.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C112(H112), C102(H102), C211(H211), C4(H4), C103(H103), C104(H104),
 C3(H3), C202(H202), C204(H204), C5(H5), C203(H203)
3.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C27(H27A,H27B,H27C), C8(H8A,H8B,H8C), C11(H11A,H11B,
 H11C), C214(H21A,H21B,H21C), C115(H11D,H11E,H11F), C111(H11G,H11H,H11I),
 C108(H10A,H10B,H10C), C114(H11J,H11K,H11L), C110(H11M,H11N,H11O), C17(H17A,
 H17B,H17C), C9(H9A,H9B,H9C), C116(H11P,H11Q,H11R), C210(H21D,H21E,H21F),
 C15(H15A,H15B,H15C), C69(H69A,H69B,H69C), C107(H10D,H10E,H10F), C12(H12A,H12B,
 H12C), C213(H21G,H21H,H21I), C207(H20A,H20B,H20C), C208(H20D,H20E,H20F)
;
_shelx_res_checksum              16355
_shelx_hkl_checksum              340