Iron-Catalyzed Trimerization of Terminal Alkynes Enabled by Pyrimidinediimine Ligands: A Regioselective Method for the Synthesis of 1,3,5-Substituted Arenes
Doll, Julianna S.; Eichelmann, Robert; Hertwig, Leif E.; Bender, Thilo; Kohler, Vincenz J.; Bill, Eckhard; Wadepohl, Hubert; Roşca, Dragoş-Adrian; ACS Catalysis  (2021) 5593–5600; doi:10.1021/acscatal.1c00978

data_4518619
_publ_section_title
;
 Iron-Catalyzed Trimerization of Terminal Alkynes Enabled by
 Pyrimidinediimine Ligands: A Regioselective Method for the Synthesis of
 1,3,5-Substituted Arenes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5593
_journal_page_last               5600
_journal_paper_doi               10.1021/acscatal.1c00978
_journal_year                    2021
_chemical_formula_moiety         'C42 H56 Fe N4, C6 H6'
_chemical_formula_sum            'C48 H62 Fe N4'
_chemical_formula_weight         750.86
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_block_code                ro_dr31
_audit_creation_date             2020-09-22
_audit_creation_method
;
encif (version 1.117)

encifer (version_id = 274361.64)

Olex2 1.3
(compiled 2020.07.31 svn.rc2a7746 for OlexSys, GUI svn.r6145)
;
_audit_update_record
'22.09.2020 11:29:01 CEST UTC+02:00  encif 1.117'
_cell_angle_alpha                90
_cell_angle_beta                 93.3137(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8259(3)
_cell_length_b                   10.7782(2)
_cell_length_c                   27.1348(5)
_cell_measurement_reflns_used    14488
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      33.0110
_cell_measurement_theta_min      2.5310
_cell_volume                     4036.82(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_publication_material
'encif (Wadepohl, 2009-19); encifer (Allen et al., 2004)'
_computing_structure_refinement  'SHELXL-20xx (Sheldrick, 2015)'
_computing_structure_solution    'DIRDIF (Beurskens et al., 1999-2008)'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.965
_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      2.00  68.00   0.50   20.00    --   31.15 -99.00 150.00  132
  2  \w     -2.00  24.00   0.50   20.00    --   31.15  82.00-116.03   52
  3  \w    -41.00  57.00   0.50   20.00    --   31.15 -38.00   0.00  196
  4  \w    -20.00  73.00   0.50   20.00    --   31.15 -99.00-120.00  186
  5  \w     11.00  38.00   0.50   20.00    --   31.15  57.00 -30.00   54
  6  \w     46.00 100.00   0.50   20.00    --   31.15  57.00 -30.00  108
  7  \w     11.00  87.00   0.50   20.00    --   31.15  57.00 -90.00  152
  8  \w     34.00  73.00   0.50   20.00    --   31.15 -99.00   0.00   78
  9  \w      2.00  41.00   0.50   20.00    --   31.15  77.00   0.00   78
 10  \w     60.00  98.00   0.50   20.00    --   31.15  77.00   0.00   76
 11  \w      3.00  97.00   0.50   20.00    --   31.15  77.00  60.00  188
 12  \w    -38.00   9.00   0.50   20.00    --   31.15 -38.00  90.00   94
 13  \w     30.00  57.00   0.50   20.00    --   31.15 -38.00  90.00   54
 14  \w      1.00  93.00   0.50   20.00    --   31.15  77.00 150.00  184
 15  \w    -41.00  52.00   0.50   20.00    --   31.15 -38.00 -90.00  186
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0385081000
_diffrn_orient_matrix_UB_12      -0.0378235000
_diffrn_orient_matrix_UB_13      -0.0074846000
_diffrn_orient_matrix_UB_21      0.0276582000
_diffrn_orient_matrix_UB_22      0.0156912000
_diffrn_orient_matrix_UB_23      0.0219442000
_diffrn_orient_matrix_UB_31      -0.0197905000
_diffrn_orient_matrix_UB_32      -0.0515367000
_diffrn_orient_matrix_UB_33      0.0121664000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0974
_diffrn_reflns_av_unetI/netI     0.0750
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            100919
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.186
_diffrn_reflns_theta_min         2.167
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.412
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.647
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.235
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.209
_exptl_crystal_size_mid          0.175
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     497
_refine_ls_number_reflns         16104
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1062
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0481P)^2^+1.7978P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1184
_refine_ls_wR_factor_ref         0.1375
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10448
_reflns_number_total             16104
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00978_si_004.cif
_cod_data_source_block           ro_dr31
_cod_original_cell_volume        4036.81(13)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4518619
_audit_block_refno               3635
_audit_block_usercomment         'DAR-RE-45, irregular, black'
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.960
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.50
_shelxl_version_number           2018/3
_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:
 C7(H7), C14(H14), C23(H23), C30(H30), C35(H35), C37(H37), C40(H40)
2.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C36(H36A,H36B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,
 H41B), C42(H42A,H42B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C17(H17), C91(H91), C92(H92), C93(H93),
 C94(H94), C95(H95), C96(H96)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.197
_oxdiff_exptl_absorpt_empirical_full_min 0.892
_shelx_res_checksum              11124
_cell_oxdiff_measurement_reflns_used 14488