Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions.
Wang, Hai-Xu; Wan, Qingyun; Wu, Kai; Low, Kam-Hung; Yang, Chen; Zhou, Cong-Ying; Huang, Jie-Sheng; Che, Chi-Ming; Journal of the American Chemical Society 141 (2019) 9027–9046; doi:10.1021/jacs.9b03357

data_4127590
_publ_section_title
;
 Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal
 Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom
 Transfer Reactions.
;
_journal_issue                   22
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9027
_journal_page_last               9046
_journal_paper_doi               10.1021/jacs.9b03357
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C66 H64 N4 O3 Ru, C6 H14'
_chemical_formula_sum            'C72 H78 N4 O3 Ru'
_chemical_formula_weight         1148.45
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.391(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.3283(8)
_cell_length_b                   18.8683(10)
_cell_length_c                   20.1718(10)
_cell_measurement_reflns_used    351
_cell_measurement_temperature    100
_cell_measurement_theta_max      65.24
_cell_measurement_theta_min      3.96
_cell_volume                     6258.4(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0615
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            24880
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        43.421
_diffrn_reflns_theta_max         43.421
_diffrn_reflns_theta_min         3.289
_exptl_absorpt_coefficient_mu    2.405
_exptl_absorpt_correction_T_max  0.7485
_exptl_absorpt_correction_T_min  0.5222
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             2424
_exptl_crystal_recrystallization_method EA/Hex
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.675
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     735
_refine_ls_number_reflns         4495
_refine_ls_number_restraints     522
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0862
_refine_ls_R_factor_gt           0.0689
_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^)+(0.1284P)^2^+12.2666P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1803
_refine_ls_wR_factor_ref         0.2020
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3508
_reflns_number_total             4495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b03357_si_002.cif
_cod_data_source_block           david271_0m-mon
_cod_database_code               4127590
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.869
_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
2. Restrained distances
 C72-C71 = C71-C70 = C69-C70 = C68-C69 = C67-C68
 1.53 with sigma of 0.02
 C67-C69
 2.5 with sigma of 0.04
 C68-C70
 2.5 with sigma of 0.04
 C69-C71
 2.5 with sigma of 0.04
 C72-C70
 2.5 with sigma of 0.04
3. Restrained planarity
 C72, C71, C70, C69, C68, C67
 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
5.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C70(H70A,H70B), C69(H69A,H69B), C68(H68A,H68B), C71(H71A,H71B)
5.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C3(H3), C4(H4), C50(H50), C14(H14), C13(H13), C8(H8), C9(H9),
 C18(H18), C54(H54), C43(H43), C46(H46), C32(H32), C30(H30), C47(H47), C29(H29),
  C33(H33), C44(H44), C22(H22), C40(H40), C36(H36), C26(H26), C39(H39),
 C25(H25), C37(H37), C23(H23)
5.c Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C62(H62A,H62B,H62C), C61(H61A,H61B,
 H61C), C34(H34A,H34B,H34C), C56(H56A,H56B,H56C), C48(H48A,H48B,H48C), C60(H60A,
 H60B,H60C), C41(H41A,H41B,H41C), C27(H27A,H27B,H27C), C64(H64A,H64B,H64C),
 C66(H66A,H66B,H66C), C72(H72A,H72B,H72C), C67(H67A,H67B,H67C)
;
_shelx_res_checksum              45606
_shelx_hkl_checksum              35128
_olex2_submission_special_instructions 'No special instructions were received'