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_4517174
_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_formula_moiety         'C49 H41 N O2 P2 Ru, 1.5(C4 H8 O)'
_chemical_formula_sum            'C55 H53 N O3.5 P2 Ru'
_chemical_formula_weight         946.99
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.907(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9019(7)
_cell_length_b                   15.2039(9)
_cell_length_c                   24.7562(15)
_cell_measurement_reflns_used    4842
_cell_measurement_temperature    99.99
_cell_measurement_theta_max      30.502
_cell_measurement_theta_min      2.365
_cell_volume                     4469.4(5)
_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      99.99
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            13699
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.573
_diffrn_reflns_theta_min         2.285
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.471
_exptl_absorpt_correction_T_max  0.513623
_exptl_absorpt_correction_T_min  0.345343
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 177229 reflections, Rint = 0.0914
 (89350 with I > 3sig(I), Rint = 0.0816)
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       needle
_exptl_crystal_F_000             1968
_exptl_crystal_recrystallization_method
'The material was recrystallised from thf by slow evaporation'
_exptl_crystal_size_max          0.317
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.063
_refine_diff_density_max         1.344
_refine_diff_density_min         -0.940
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         13699
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0435
_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^)+(0.0638P)^2^+4.0875P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1132
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11796
_reflns_number_total             13699
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04592_si_011.cif
_cod_data_source_block           0473_cg_0m_4
_cod_original_formula_sum        'C55 H53 N O3.50 P2 Ru'
_cod_database_code               4517174
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.865
_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. Shared sites
{C1A, N1B}
{N1A, C1B}
3. Uiso/Uaniso restraints and constraints
Uanis(C1A) = Uanis(N1B)
Uanis(N1A) = Uanis(C1B)
4. Rigid body (RIGU) restrains
 O4, C54, C55, C56, C57
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(N1B)=Sof(C1B)=1-FVAR(1)
 Sof(N1A)=Sof(C1A)=FVAR(1)
 Fixed Sof: C55(0.5) H55A(0.5) H55B(0.5) O4(0.5) C54(0.5) H54A(0.5) H54B(0.5)
 C56(0.5) H56A(0.5) H56B(0.5) C57(0.5) H57A(0.5) H57B(0.5)
6.a Free rotating group:
 C55(O4,C54,C56,C57)
6.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C54(H54A,H54B), C56(H56A,H56B), C57(H57A,H57B), C50(H50A,
 H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), 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), C31(H31), C32(H32),
 C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C43(H43), C44(H44), C45(H45), C46(H46), C47(H47)
6.d Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C)
;
_shelx_res_checksum              95369
_shelx_hkl_checksum              92649
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder oil'
_olex2_submission_special_instructions 'No special instructions were received'