Ruthenium-Catalyzed Hydroamination of Unactivated Terminal Alkenes with Stoichiometric Amounts of Alkene and an Ammonia Surrogate by Sequential Oxidation and Reduction.
Ma, Senjie; Hill, Christopher K.; Olen, Casey L.; Hartwig, John F.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c11043

data_4135479
_publ_section_title
;
 Ruthenium-Catalyzed Hydroamination of Unactivated Terminal Alkenes with
 Stoichiometric Amounts of Alkene and an Ammonia Surrogate by Sequential
 Oxidation and Reduction.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c11043
_journal_year                    2020
_chemical_formula_moiety
'C21.5 H45 F10.5 N1.75 O7.25 P3 Ru S3.5, 0.25(C2 F6 N1 O4 S2)'
_chemical_formula_sum            'C22 H45 F12 N2 O8.25 P3 Ru S4'
_chemical_formula_weight         1019.82
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.423(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.433(3)
_cell_length_b                   18.944(5)
_cell_length_c                   18.126(5)
_cell_measurement_reflns_used    9929
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.33
_cell_measurement_theta_min      2.25
_cell_volume                     3924.6(18)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-I CCd'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0671
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 1.000
_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       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            122529
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.384
_diffrn_reflns_theta_min         1.555
_diffrn_source                   'fine focus sealed tube'
_exptl_absorpt_coefficient_mu    0.836
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_correction_T_min  0.836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.726
_exptl_crystal_description       prism
_exptl_crystal_F_000             2072
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.940
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     605
_refine_ls_number_reflns         7197
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0198P)^2^+10.2871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0761
_refine_ls_wR_factor_ref         0.0786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6539
_reflns_number_total             7197
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11043_si_002.cif
_cod_data_source_block           Hartwig156
_cod_database_code               4135479
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.952
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S3A-C21A
 1.84 with sigma of 0.005
 F7A-C21A
 1.32 with sigma of 0.005
 F9A-C21A
 1.32 with sigma of 0.005
 F8A-C21A
 1.32 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(O8) = Uanis(O8A)
Uanis(O5) = Uanis(O9)
Uanis(C22) = Uanis(C22A)
4. Others
 Sof(C21A)=Sof(C22A)=Sof(N2A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=Sof(O9)=
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(S3A)=Sof(S4A)=1-
 FVAR(1)
 Sof(C21)=Sof(C22)=Sof(N2)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=Sof(F7)=Sof(F8)=
 Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(S3)=Sof(S4)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,
 H11B), C13(H13A,H13B), C15(H15A,H15B), C17(H17A,H17B)
5.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              8091
_shelx_hkl_checksum              311
_olex2_submission_special_instructions 'No special instructions were received'