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_7714865
_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         'C24 H25 N5 Rh, F6 P, C2 H3 N'
_chemical_formula_sum            'C26 H28 F6 N6 P Rh'
_chemical_formula_weight         672.42
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                71.972(5)
_cell_angle_beta                 85.744(6)
_cell_angle_gamma                74.916(5)
_cell_formula_units_Z            2
_cell_length_a                   8.6913(8)
_cell_length_b                   11.5969(12)
_cell_length_c                   13.7677(14)
_cell_measurement_reflns_used    12505
_cell_measurement_temperature    115
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      3.00
_cell_volume                     1274.1(2)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      115
_diffrn_detector                 'Image Plate'
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'R-AXIS RAPID'
_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  0.0285
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12505
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.427
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.807
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7259
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   ABCOR(Rigaku,1995)
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.753
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.783
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         5819
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0344
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0288P)^2^+1.1106P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0638
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5241
_reflns_number_total             5819
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03429a2.cif
_cod_data_source_block           shelx_trans
_cod_depositor_comments
'Adding full bibliography for 7714865--7714866.cif.'
_cod_database_code               7714865
_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:
 C12(H12), C19(H19), C5(H5), C8(H8), C6(H6), C18(H18), C17(H17), C16(H16),
 C7(H7)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C3(H3A,H3B,H3C), C11(H11A,H11B,H11C), C24(H24A,H24B,
 H24C), C14(H14A,H14B,H14C), C26(H26A,H26B,H26C)
;
_olex2_submission_special_instructions 'No special instructions were received'