A rhodium(II)/rhodium(III) redox couple for C-H bond amination with alkylazides: a rhodium(III)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand.
Sugimoto, Hideki; Sakaida, Megumu; Shiota, Yoshihito; Miyanishi, Mayuko; Morimoto, Yuma; Yoshizawa, Kazunari; Itoh, Shinobu; Dalton transactions (Cambridge, England : 2003) 53 (2024) 1607–1615; doi:10.1039/d3dt03429a

data_7714866
_publ_section_title
;
 A rhodium(II)/rhodium(III) redox couple for C-H bond amination with
 alkylazides: a rhodium(III)-nitrenoid intermediate with a tetradentate
 [14]-macrocyclic ligand.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1607
_journal_page_last               1615
_journal_paper_doi               10.1039/d3dt03429a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C27 H27 N5 Rh, F6 P'
_chemical_formula_sum            'C27 H27 F6 N5 P Rh'
_chemical_formula_weight         669.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-02-08 deposited with the CCDC.	2023-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.183(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.4897(13)
_cell_length_b                   20.8788(18)
_cell_length_c                   18.4267(19)
_cell_measurement_reflns_used    23608
_cell_measurement_temperature    115
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      .033
_cell_volume                     5137.0(9)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      115
_diffrn_detector                 'Image Plate'
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0593
_diffrn_reflns_av_unetI/netI     0.0552
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23608
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         1.810
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.800
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5374
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.731
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.907
_refine_diff_density_min         -1.505
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     365
_refine_ls_number_reflns         5880
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0618
_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^)+85.5509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1263
_refine_ls_wR_factor_ref         0.1365
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4545
_reflns_number_total             5880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03429a2.cif
_cod_data_source_block           shelx_trans_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7714865--7714866.cif.'
_cod_database_code               7714866
_shelx_shelxl_version_number     2018/1
_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 Ternary CH refined with riding coordinates:
 C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C12(H12), C24(H24), C27(H27), C16(H16), C25(H25), C6(H6), C7(H7),
 C5(H5), C17(H17), C26(H26), C8(H8), C18(H18), C19(H19)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C22(H22A,H22B,H22C)
;
_olex2_submission_special_instructions 'No special instructions were received'