Late-Stage Diversification by Selectivity Switch in meta-C‒H Activation: Evidence for Singlet Stabilization
Korvorapun, Korkit; Kuniyil, Rositha; Ackermann, Lutz; ACS Catalysis  (2019) 435–; doi:10.1021/acscatal.9b04592

data_4517173
_publ_section_title
;
 Late-Stage Diversification by Selectivity Switch in meta-C--H Activation:
 Evidence for Singlet Stabilization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              435
_journal_paper_doi               10.1021/acscatal.9b04592
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H29 N2 O2 P Ru'
_chemical_formula_sum            'C33 H29 N2 O2 P Ru'
_chemical_formula_weight         617.62
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2264(8)
_cell_length_b                   9.3716(4)
_cell_length_c                   17.7053(10)
_cell_measurement_reflns_used    9501
_cell_measurement_temperature    100.1
_cell_measurement_theta_max      31.517
_cell_measurement_theta_min      2.510
_cell_volume                     2692.4(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.1
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            57514
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.522
_diffrn_reflns_theta_min         2.301
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.676
_exptl_absorpt_correction_T_max  0.3919
_exptl_absorpt_correction_T_min  0.3510
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1141 before and 0.0472 after correction. The Ratio of minimum to maximum transmission is 0.8956. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 4203 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.032(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         8977
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0160
_refine_ls_R_factor_gt           0.0155
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0216P)^2^+0.7093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0408
_refine_ls_wR_factor_ref         0.0412
_reflns_Friedel_coverage         0.944
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                8842
_reflns_number_total             8977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04592_si_012.cif
_cod_data_source_block           pna21
_cod_database_code               4517173
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.820
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22),
  C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29)
2.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              37570
_shelx_hkl_checksum              41953
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in NVH oil'
_olex2_submission_special_instructions 'No special instructions were received'