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_4132507
_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         'C48 H28 Cl F8 N4 O Ru, 0.5(C4 H8 O)'
_chemical_formula_sum            'C50 H32 Cl F8 N4 O1.5 Ru'
_chemical_formula_weight         1001.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-09-24
_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
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.4235(5)
_cell_length_b                   20.7153(9)
_cell_length_c                   39.4855(17)
_cell_measurement_reflns_used    9521
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.23
_cell_measurement_theta_min      2.41
_cell_volume                     9343.9(7)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.987
_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_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         67.082
_diffrn_reflns_theta_min         2.238
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.886
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.5470
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1138 before and 0.0663 after correction. The Ratio of minimum to maximum transmission is 0.7265. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       block
_exptl_crystal_F_000             4040
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.204
_refine_diff_density_min         -0.459
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Flack x determined using 5751 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.499(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1157
_refine_ls_number_reflns         16366
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.0674
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0901P)^2^+11.7332P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1668
_refine_ls_wR_factor_ref         0.1774
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    0.973
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                13425
_reflns_number_total             16366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b04470_si_004.cif
_cod_data_source_block           complex_3
_cod_original_formula_sum        'C50 H32 Cl F8 N4 O1.50 Ru'
_cod_database_code               4132507
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C47-C48 = C46-C47 = C45-C46
 1.54 with sigma of 0.02
 C45A-C46A = C46A-C47A = C47A-C48A
 1.54 with sigma of 0.02
 C46A-C48A = C47A-C45A = C45-C47 = C46-C48
 2.52 with sigma of 0.04
 F12A-C76A \\sim F12-C76 \\sim F11-C80 \\sim F11A-C80A
 with sigma of 0.02
3. Restrained planarity
 F11, F12, C75, C76, C77, C78, C79, C80
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O1 \\sim C46 \\sim C45A \\sim C46A \\sim C48A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02
F11 \\sim F12 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C45) = Uanis(C45A)
Uanis(C46) = Uanis(C46A)
Uanis(C47) = Uanis(C47A)
Uanis(C48) = Uanis(C48A)
Uanis(C75) = Uanis(C75A)
Uanis(C80) = Uanis(C80A)
Uanis(C79) = Uanis(C79A)
Uanis(C78) = Uanis(C78A)
Uanis(C77) = Uanis(C77A)
Uanis(C76) = Uanis(C76A)
Uanis(F12) = Uanis(F12A)
Uanis(F11) = Uanis(F11A)
5. Others
 Sof(C45A)=Sof(H45c)=Sof(H45d)=Sof(C46A)=Sof(H46c)=Sof(H46d)=Sof(C47A)=
 Sof(H47c)=Sof(H47d)=Sof(C48A)=Sof(H48c)=Sof(H48d)=1-FVAR(1)
 Sof(C47)=Sof(H47a)=Sof(H47b)=Sof(C48)=Sof(H48a)=Sof(H48b)=Sof(C46)=Sof(H46a)=
 Sof(H46b)=Sof(C45)=Sof(H45a)=Sof(H45b)=FVAR(1)
 Sof(C75A)=Sof(C76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=Sof(C79A)=
 Sof(H79A)=Sof(C80A)=Sof(F12A)=Sof(F11A)=1-FVAR(2)
 Sof(C75)=Sof(C80)=Sof(C79)=Sof(H79)=Sof(C78)=Sof(H78)=Sof(C77)=Sof(H77)=
 Sof(C76)=Sof(F11)=Sof(F12)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C94(H94a,H94b), C47(H47a,H47b), C48(H48a,H48b), C93(H93a,H93b), C96(H96a,
 H96b), C95(H95a,H95b), C46(H46a,H46b), C45(H45a,H45b), C99(H99a,H99b),
 C98(H98a,H98b), C97(H97a,H97b), C100(H10a,H10b), C45A(H45c,H45d), C46A(H46c,
 H46d), C47A(H47c,H47d), C48A(H48c,H48d)
6.b Aromatic/amide H refined with riding coordinates:
 C41(H41), C42(H42), C43(H43), C7(H7), C12(H12), C8(H8), C13(H13), C66(H66),
 C50(H50), C18(H18), C65(H65), C51(H51), C60(H60), C17(H17), C61(H61), C2(H2),
 C85(H85), C83(H83), C84(H84), C73(H73), C56(H56), C71(H71), C72(H72), C31(H31),
  C55(H55), C3(H3), C89(H89), C30(H30), C79(H79), C78(H78), C77(H77), C91(H91),
 C90(H90), C29(H29), C37(H37), C25(H25), C24(H24), C36(H36), C35(H35), C23(H23),
  C77A(H77A), C78A(H78A), C79A(H79A)
6.c Fitted hexagon refined as free rotating group:
 C39(C40,C41,C42,C43,C44), C75(C80,C79,C78,C77,C76), C75A(C76A,C77A,C78A,C79A,
 C80A)
;
_shelx_hkl_checksum              70401
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20