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_4132356
_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         'C64 H68 N5 O2 Rh, 2(C4 H8 O)'
_chemical_formula_sum            'C72 H84 N5 O4 Rh'
_chemical_formula_weight         1186.35
_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     direct
_audit_creation_date             2015-08-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                93.224(3)
_cell_angle_beta                 99.919(4)
_cell_angle_gamma                93.288(5)
_cell_formula_units_Z            1
_cell_length_a                   10.430(3)
_cell_length_b                   11.159(3)
_cell_length_c                   13.768(4)
_cell_measurement_reflns_used    5441
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4843
_cell_measurement_theta_min      2.2717
_cell_volume                     1572.3(8)
_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 0.991
_diffrn_measured_fraction_theta_max 0.987
_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: 180.0000
	             XTD: 45.1211
	          2theta: -20.1797
scan:
	Number of images: 356
	           Slice: -110.0000 - 68.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 45.1211
	          2theta: -20.1797
scan:
	Number of images: 338
	           Slice: -110.0000 - 59.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 45.1211
	          2theta: -20.1797
;
_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      -0.0405
_diffrn_orient_matrix_UB_12      0.0474
_diffrn_orient_matrix_UB_13      -0.0750
_diffrn_orient_matrix_UB_21      -0.0753
_diffrn_orient_matrix_UB_22      -0.0492
_diffrn_orient_matrix_UB_23      0.0016
_diffrn_orient_matrix_UB_31      -0.0387
_diffrn_orient_matrix_UB_32      0.0513
_diffrn_orient_matrix_UB_33      0.0364
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17899
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.940
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.324
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9010
_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    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             628
_exptl_crystal_size_max          0.413
_exptl_crystal_size_mid          0.329
_exptl_crystal_size_min          0.294
_refine_diff_density_max         1.617
_refine_diff_density_min         -0.620
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.310
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         7128
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.344
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0504
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1564
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7018
_reflns_number_total             7128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b03029_si_002.cif
_cod_data_source_block           (TMP)RhCONHPr
_cod_original_cell_volume        1572.2(8)
_cod_database_code               4132356
_shelxl_version_number           2013-4
_diffrn_number_total             7135
_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. Uiso/Uaniso restraints and constraints
Uanis(C33) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
3. Others
 Fixed Sof: O1(0.5) N31(0.5) H31(0.5) C29(0.5) C30(0.5) H30A(0.5) H30B(0.5)
 C31(0.5) H31A(0.5) H31B(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) C39(0.5)
 H39A(0.5) H39B(0.5) C37(0.5) H37A(0.5) H37B(0.5) O2(0.5) C38(0.5) H38A(0.5)
 H38B(0.5) C40(0.5) H40A(0.5) H40B(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,
 H35B), C36(H36A,H36B), C39(H39A,H39B), C37(H37A,H37B), C38(H38A,H38B),
 C40(H40A,H40B)
4.b Me refined with riding coordinates:
 C26(H26A,H26B,H26C)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C13(H13), C15(H15), C22(H22), C24(H24),
 N31(H31)
4.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              53686
_shelx_hkl_checksum              94435
_olex2_submission_special_instructions 'No special instructions were received'