Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [Ru<sup>V</sup>(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations.
Shing, Ka-Pan; Cao, Bei; Liu, Yungen; Lee, Hung Kay; Li, Ming-De; Phillips, David Lee; Chang, Xiao-Yong; Che, Chi-Ming; Journal of the American Chemical Society 140 (2018) 7032–7042; doi:10.1021/jacs.8b04470

data_4132508
_publ_section_title
;
 Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at
 Room Temperature and [Ru<sup>V</sup>(Por)(O)(Ph)] Intermediate by
 Spectroscopic Analysis and Density Functional Theory Calculations.
;
_journal_issue                   22
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7032
_journal_page_last               7042
_journal_paper_doi               10.1021/jacs.8b04470
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C50 H27 F8 N4 O Ru, H2 O'
_chemical_formula_sum            'C50 H29 F8 N4 O2 Ru'
_chemical_formula_weight         970.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.0865(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0727(13)
_cell_length_b                   12.7833(8)
_cell_length_c                   20.2135(13)
_cell_measurement_reflns_used    9883
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.10
_cell_measurement_theta_min      4.17
_cell_volume                     4901.6(5)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28785
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.467
_diffrn_reflns_theta_min         4.170
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.207
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.5067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1315 before and 0.0964 after correction.
The Ratio of minimum to maximum transmission is 0.6730.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       plate
_exptl_crystal_F_000             1956
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
;
_refine_diff_density_max         1.444
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         4289
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0574
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0688P)^2^+31.2264P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1572
_refine_ls_wR_factor_ref         0.1598
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3915
_reflns_number_total             4289
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b04470_si_003.cif
_cod_data_source_block           complex_2
_cod_database_code               4132508
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 H2A-F2
 2.12 with sigma of 0.04
 H1A-O2
 1.98 with sigma of 0.04
 C22-C17 \\sim C22A-C17A \\sim C18A-C17A \\sim C18-C17
 with sigma of 0.02
3. Rigid bond restraints
 C23, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C17A \\sim C18A \\sim C19A \\sim C20A \\sim C21A \\sim C22A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C23 \\sim C28: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C17A) = Uanis(C17)
Uanis(C22A) = Uanis(C22)
Uanis(C21A) = Uanis(C21)
Uanis(C20A) = Uanis(C20)
Uanis(C19A) = Uanis(C19)
Uanis(C18A) = Uanis(C18)
Uanis(F3A) = Uanis(F3)
Uanis(C23) = Uanis(O1)
Uanis(C28) = Uanis(C24)
Uanis(C27) = Uanis(C25)
Uanis(F4A) = Uanis(F4)
5. Others
 Sof(F3)=Sof(F4)=Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=Sof(C22)=1-FVAR(1)
 Sof(F3A)=Sof(F4A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=
 Sof(C21A)=Sof(H21A)=Sof(C22A)=FVAR(1)
 Fixed Sof: O1(0.5) H1A(0.5) H1B(0.5) O2(0.5) H2A(0.5) H2B(0.5) C24(0.5)
 H24(0.5) C23(0.5) C28(0.5) H28(0.5) C27(0.5) H27(0.5) C26(0.5) H26(0.5)
 C25(0.5) H25(0.5)
6.a Free rotating group:
 O1(H1A,H1B), O2(H2A,H2B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C7(H7), C13(H13), C14(H14), C15(H15), C19(H19),
 C20(H20), C21(H21), C24(H24), C28(H28), C27(H27), C26(H26), C25(H25),
 C19A(H19A), C20A(H20A), C21A(H21A)
6.c Fitted hexagon refined as free rotating group:
 C24(C23,C28,C27,C26,C25)
;
_olex2_submission_special_instructions 'No special instructions were received'