Production of Formamides from CO and Amines Induced by Porphyrin Rhodium(II) Metalloradical.
Zhang, Jiajing; Zhang, Wentao; Xu, Minghui; Zhang, Yang; Fu, Xuefeng; Fang, Huayi; Journal of the American Chemical Society 140 (2018) 6656–6660; doi:10.1021/jacs.8b03029

data_4132357
_publ_section_title
;
 Production of Formamides from CO and Amines Induced by Porphyrin
 Rhodium(II) Metalloradical.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6656
_journal_page_last               6660
_journal_paper_doi               10.1021/jacs.8b03029
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C52 H44 N5 O2 Rh'
_chemical_formula_sum            'C52 H44 N5 O2 Rh'
_chemical_formula_weight         873.83
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                62.96(3)
_cell_angle_beta                 75.66(3)
_cell_angle_gamma                68.08(3)
_cell_formula_units_Z            1
_cell_length_a                   9.813(2)
_cell_length_b                   11.262(2)
_cell_length_c                   11.590(2)
_cell_measurement_reflns_used    4007
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4836
_cell_measurement_theta_min      2.1298
_cell_volume                     1053.6(5)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 40.0977
	          2theta: -19.8472
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 40.0977
	          2theta: -19.8472
scan:
	Number of images: 344
	           Slice: -110.0000 - 62.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 0.0000
	             XTD: 40.0977
	          2theta: -19.8472
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.0132
_diffrn_orient_matrix_UB_12      -0.0191
_diffrn_orient_matrix_UB_13      0.1079
_diffrn_orient_matrix_UB_21      -0.1023
_diffrn_orient_matrix_UB_22      -0.0065
_diffrn_orient_matrix_UB_23      -0.0209
_diffrn_orient_matrix_UB_31      0.0510
_diffrn_orient_matrix_UB_32      -0.0775
_diffrn_orient_matrix_UB_33      -0.0294
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13251
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.464
_diffrn_reflns_theta_min         2.588
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       plate
_exptl_crystal_F_000             452
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.824
_refine_diff_density_min         -0.674
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     323
_refine_ls_number_reflns         4803
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0252P)^2^+1.2861P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0943
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4770
_reflns_number_total             4803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b03029_si_003.cif
_cod_data_source_block           (TPP)RhCONHPr
_cod_database_code               4132357
_diffrn_number_total             4811
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N3-C23 = N3-C24
 1.47 with sigma of 0.01
 O1-C23
 1.23 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N3 \\sim C24 \\sim C23 \\sim O1 \\sim C27 \\sim C25 \\sim C28 \\sim C26 \\sim
C29 \\sim C30 \\sim O2: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(O2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: N3(0.5) H3(0.5) C24(0.5) H24A(0.5) H24B(0.5) C23(0.5) O1(0.5)
 C27(0.5) H27A(0.5) H27B(0.5) C25(0.5) H25A(0.5) H25B(0.5) C28(0.5) H28A(0.5)
 H28B(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 C30(0.5) H30A(0.5) H30B(0.5) O2(0.5)
5.a Riding coordinates:
 N3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C27(H27A,H27B), C25(H25A,H25B), C28(H28A,H28B), C29(H29A,
 H29B), C30(H30A,H30B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C0AA(H0AA), C13(H13), C14(H14), C11(H11), C8(H8), C22(H22), C20(H20),
 C7(H7), C18(H18), C10(H10), C19(H19), C21(H21), C9(H9)
5.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C)
;
_shelx_res_checksum              4298
_shelx_hkl_checksum              81778
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'