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_4132509
_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         'C54 H35 Cl8 N4 O Ru, C4 H10 O, C3 H7'
_chemical_formula_sum            'C61 H52 Cl8 N4 O2 Ru'
_chemical_formula_weight         1257.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2014-06-20
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.18 svn.r2945 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.011(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5729(12)
_cell_length_b                   21.6205(16)
_cell_length_c                   21.910(2)
_cell_measurement_reflns_used    2707
_cell_measurement_temperature    100
_cell_measurement_theta_max      65.359
_cell_measurement_theta_min      29.465
_cell_volume                     5933.1(9)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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 0.951
_diffrn_measured_fraction_theta_max 0.965
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0809
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.951
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            72964
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.005
_diffrn_reflns_theta_min         2.877
_exptl_absorpt_coefficient_mu    5.814
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.4553
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1325 before and 0.0983 after correction.
The Ratio of minimum to maximum transmission is 0.6047.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       prism
_exptl_crystal_F_000             2568
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.556
_refine_diff_density_min         -1.292
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     707
_refine_ls_number_reflns         10195
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0641
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0748P)^2^+29.9429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1642
_refine_ls_wR_factor_ref         0.1784
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8606
_reflns_number_total             10195
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b04470_si_002.cif
_cod_data_source_block           complex_1
_cod_original_cell_volume        5932.9(9)
_cod_database_code               4132509
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.722
_shelx_estimated_absorpt_t_min   0.324
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C59-C60 = C61-C60 = C59_$1-C59
 1.54 with sigma of 0.01
3. Rigid bond restraints
 C61, C60, C59
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C61 \\sim C60 \\sim C59: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C51A)=
 Sof(H51C)=Sof(H51D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=1-FVAR(1)
 Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(C53)=Sof(H53A)=Sof(H53B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B), C51(H51A,H51B), C53(H53A,H53B), C51A(H51C,
 H51D), C53A(H53C,H53D), C60(H60A,H60B), C59(H59A,H59B)
6.b Me refined with riding coordinates:
 C54(H54A,H54B,H54C), C54(H54D,H54E,H54F), C52(H52A,H52B,H52C), C52(H52D,H52E,
 H52F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C46(H46), C8(H8), C12(H12), C13(H13), C17(H17), C31(H31), C3(H3),
 C18(H18), C36(H36), C25(H25), C23(H23), C41(H41), C50(H50), C35(H35), C49(H49),
  C7(H7), C48(H48), C37(H37), C24(H24), C42(H42), C43(H43), C47(H47), C30(H30),
 C29(H29)
6.d Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C58(H58A,H58B,H58C), C61(H61A,H61B,H61C)
;
_olex2_submission_special_instructions 'No special instructions were received'