N-Trifluoromethyl NHC Ligands Provide Selective Ruthenium Metathesis Catalysts
Engl, Pascal S.; Fedorov, Alexey; Copéret, Christophe; Togni, Antonio; Organometallics 35 (2016) 887–; doi:10.1021/acs.organomet.6b00028

data_4088369
_publ_section_title
;
 N-Trifluoromethyl NHC Ligands Provide Selective Ruthenium Metathesis
 Catalysts
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              887
_journal_paper_doi               10.1021/acs.organomet.6b00028
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C39 H48 Cl2 F3 N2 P Ru, C H2 Cl2'
_chemical_formula_sum            'C40 H50 Cl4 F3 N2 P Ru'
_chemical_formula_weight         889.66
_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     direct
_audit_creation_date             2015-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.906(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6135(17)
_cell_length_b                   9.9787(17)
_cell_length_c                   43.076(7)
_cell_measurement_reflns_used    9954
_cell_measurement_temperature    101.7
_cell_measurement_theta_max      30.67
_cell_measurement_theta_min      2.49
_cell_volume                     4131.8(12)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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      101.8
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1048
_diffrn_reflns_av_unetI/netI     0.0908
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       60
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            61512
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.030
_diffrn_reflns_theta_min         2.307
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.721
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.5671
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0868 before and 0.0687 after correction.
The Ratio of minimum to maximum transmission is 0.7597.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       prism
_exptl_crystal_F_000             1832
_exptl_crystal_recrystallization_method CH2Cl2/hexane
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.322
_exptl_crystal_size_min          0.149
_refine_diff_density_max         0.934
_refine_diff_density_min         -1.078
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         12056
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0675
_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^)+(0.0247P)^2^+12.7237P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1063
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8541
_reflns_number_total             12056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00028_si_002.cif
_cod_data_source_block           pse-nhc-143
_cod_database_code               4088369
_shelxl_version_number           2012-9
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.799
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 C16, C21, C20, C19, C18, C17
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C19A, C18A, C20A, C17A, C21A, C16A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C16 \\sim C16A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Rigid body (RIGU) restrains
 C16, C21, C20, C19, C18, C17
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C19A, C18A, C20A, C17A, C21A, C16A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H15A)=Sof(C16)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=Sof(C19)=Sof(H19)=
 Sof(C18)=Sof(H18)=Sof(C17)=Sof(H17)=1-FVAR(1)
 Sof(H15)=Sof(C16A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=Sof(C19A)=
 Sof(H19A)=Sof(C18A)=Sof(H18A)=Sof(C17A)=Sof(H17A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C22(H22), C28(H28), C34(H34)
6.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C40(H40A,H40B), C26(H26A,H26B), C32(H32A,H32B), C31(H31A,
 H31B), C38(H38A,H38B), C27(H27A,H27B), C25(H25A,H25B), C29(H29A,H29B),
 C30(H30A,H30B), C37(H37A,H37B), C36(H36A,H36B), C23(H23A,H23B), C35(H35A,H35B),
  C24(H24A,H24B), C39(H39A,H39B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C11(H11), C4(H4), C3(H3), C12(H12), C15(H15), C15(H15A),
 C6(H6), C13(H13), C14(H14), C21A(H21A), C20A(H20A), C19A(H19A), C18A(H18A),
 C17A(H17A), C21(H21), C20(H20), C19(H19), C18(H18), C17(H17)
6.d Fitted hexagon refined as free rotating group:
 C16A(C21A,C20A,C19A,C18A,C17A), C16(C21,C20,C19,C18,C17)
;
_shelx_res_checksum              89110
_shelx_hkl_checksum              17997
_olex2_date_sample_data_collection 2015-02-12
_olex2_submission_special_instructions 'No special instructions were received'