Dehydrogenative Synthesis of Carbamates from Formamides and Alcohols Using a Pincer-Supported Iron Catalyst
Townsend, Tanya M.; Bernskoetter, Wesley H.; Hazari, Nilay; Mercado, Brandon Q.; ACS Catalysis 11 (2021) 10614–10624; doi:10.1021/acscatal.1c02718

data_4518986
_publ_section_title
;
 Dehydrogenative Synthesis of Carbamates from Formamides and Alcohols
 Using a Pincer-Supported Iron Catalyst
;
_journal_issue                   16
_journal_name_full               'ACS Catalysis'
_journal_page_first              10614
_journal_page_last               10624
_journal_paper_doi               10.1021/acscatal.1c02718
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C25 H44 Fe N2 O2 P2'
_chemical_formula_sum            'C25 H44 Fe N2 O2 P2'
_chemical_formula_weight         522.41
_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
_audit_creation_date             2021-05-18
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                74.165(5)
_cell_angle_beta                 79.061(5)
_cell_angle_gamma                83.962(5)
_cell_formula_units_Z            2
_cell_length_a                   8.1307(5)
_cell_length_b                   13.0711(8)
_cell_length_c                   13.4922(9)
_cell_measurement_reflns_used    3470
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.1840
_cell_measurement_theta_min      2.5950
_cell_volume                     1352.27(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_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      293(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -120.00  60.00   1.00   40.00    --  -29.30  54.00 240.00  180
  2  \w   -120.00 -30.00   1.00   40.00    --  -29.30  54.00   0.00   90
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Mercury275R CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0955
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6561
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.622
_exptl_absorpt_coefficient_mu    0.699
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84093
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       Block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.777
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         5445
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1034
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0796P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1450
_refine_ls_wR_factor_ref         0.1733
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3649
_reflns_number_total             5445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02718_si_002.cif
_cod_data_source_block           '_Compound6Bn'
_cod_database_code               4518986
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.818
_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.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C20(H20), C23(H23)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C)
;
_shelx_res_checksum              71105
_shelx_hkl_checksum              29667
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;