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_4518621
_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_sum            'C132 H204 Fe2 N12 Na2 O4'
_chemical_formula_weight         2180.74
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ro_jd1
_audit_creation_date             2021-01-08
_audit_creation_method
;
encif (version 1.124)

encifer (version_id = 270009.64)

Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6226)
;
_audit_update_record
'08.01.2021 11:30:09 CET UTC+01:00  encif 1.124'
_cell_angle_alpha                89.690(2)
_cell_angle_beta                 83.236(3)
_cell_angle_gamma                73.710(3)
_cell_formula_units_Z            1
_cell_length_a                   14.3281(6)
_cell_length_b                   15.1547(5)
_cell_length_c                   15.3273(4)
_cell_measurement_reflns_used    12266
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      69.3920
_cell_measurement_theta_min      4.0580
_cell_volume                     3171.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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    'SIR2019 (Giacovazzo et al., 2019)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.980
_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    -27.00  73.00   1.00    7.50    --    0.00  38.00-180.00  100
  2  \w    -27.00  73.00   1.00    7.50    --    0.00  38.00   0.00  100
  3  \w    -22.00  69.00   1.00    7.50    --    0.00  57.00-120.00   91
  4  \w    -22.00  69.00   1.00    7.50    --    0.00  57.00  60.00   91
  5  \w    -33.00  18.00   1.00    7.50    --   12.00 101.00 132.07   51
  6  \w    -27.00   8.00   1.00    7.50    --   24.00 113.00 -10.87   35
  7  \w    -32.00  -4.00   1.00   12.50    --   28.00 128.00-167.18   28
  8  \w    -19.00   9.00   1.00   12.50    --   32.00 112.00 -48.76   28
  9  \w    -21.00   5.00   1.00   12.50    --   32.00 117.00 -89.18   26
 10  \w      6.00  33.00   1.00   12.50    --   44.00  88.00  -5.77   27
 11  \w      5.00  32.00   1.00   12.50    --   44.00  90.00-102.18   27
 12  \w      6.00  33.00   1.00   12.50    --   44.00  89.00 136.33   27
 13  \w     14.00  45.00   1.00   12.50    --   48.00  81.00 133.80   31
 14  \w     14.00  45.00   1.00   12.50    --   48.00  81.00 -27.67   31
 15  \w     14.00  45.00   1.00   12.50    --   48.00  82.00  67.73   31
 16  \w     13.00  40.00   1.00   12.50    --   48.00  83.00-141.12   27
 17  \w     14.00  45.00   1.00   12.50    --   48.00  82.00 -82.70   31
 18  \w     18.00  45.00   1.00   12.50    --   52.00  81.00 -88.81   27
 19  \w     21.00 123.00   1.00   12.50    --   52.00  76.00 162.51  102
 20  \w     18.00  45.00   1.00   12.50    --   52.00  81.00  84.27   27
 21  \w     18.00  45.00   1.00   12.50    --   52.00  82.00  12.52   27
 22  \w     19.00  45.00   1.00   12.50    --   52.00  80.00-167.85   26
 23  \w     22.00 125.00   1.00   12.50    --   54.00  77.00-150.00  103
 24  \w     22.00 125.00   1.00   12.50    --   54.00  77.00  60.00  103
 25  \w    -15.00  76.00   1.00   12.50    --   54.00 -57.00  60.00   91
 26  \w    -17.00  86.00   1.00   12.50    --   54.00 -77.00-180.00  103
 27  \w     22.00  58.00   1.00   12.50    --   54.00  77.00-120.00   36
 28  \w     23.00 105.00   1.00   12.50    --   54.00-125.00  60.00   82
 29  \w     25.00  52.00   1.00   12.50    --   54.00  77.00 150.00   27
 30  \w     27.00  54.00   1.00   12.50    --   54.00  77.00 120.00   27
 31  \w     79.00 121.00   1.00   12.50    --   56.00  77.00 168.10   42
 32  \w     30.00  57.00   1.00   12.50    --   56.00  70.00 142.07   27
 33  \w     26.00  51.00   1.00   12.50    --   56.00  76.00 -63.69   25
 34  \w     27.00  54.00   1.00   12.50    --   56.00  76.00  -0.23   27
 35  \w     27.00  54.00   1.00   12.50    --   56.00  76.00  16.46   27
 36  \w     26.00  53.00   1.00   12.50    --   56.00  77.00 168.10   27
 37  \w     29.00  58.00   1.00   12.50    --   60.00  77.00 -88.49   29
 38  \w     28.00  58.00   1.00   12.50    --   60.00  77.00  84.33   30
 39  \w     32.00  86.00   1.00   12.50    --   60.00  73.00-111.27   54
 40  \w     35.00  62.00   1.00   12.50    --   60.00  76.00  61.08   27
 41  \w     78.00 105.00   1.00   12.50    --   60.00  76.00 -42.16   27
 42  \w     29.00  54.00   1.00   12.50    --   60.00  77.00-138.05   25
 43  \w     28.00  55.00   1.00   12.50    --   60.00  77.00  30.77   27
 44  \w     29.00  56.00   1.00   12.50    --   60.00  76.00 -42.16   27
 45  \w     56.00  83.00   1.00   12.50    --   60.00  77.00  30.77   27
 46  \w     29.00  55.00   1.00   12.50    --   60.00  76.00-175.06   26
 47  \w     33.00  60.00   1.00   12.50    --   60.00  75.00   2.78   27
 48  \w     34.00  61.00   1.00   12.50    --   64.00  77.00 -37.16   27
 49  \w     38.00  70.00   1.00   12.50    --   64.00  71.00 155.41   32
 50  \w     36.00  64.00   1.00   12.50    --   64.00  73.00  98.15   28
 51  \w     37.00  65.00   1.00   12.50    --   64.00  73.00 133.74   28
 52  \w     33.00  58.00   1.00   12.50    --   64.00  77.00  18.13   25
 53  \w     37.00  73.00   1.00   12.50    --   68.00  75.00-176.97   36
 54  \w     78.00 121.00   1.00   12.50    --   68.00  75.00-176.97   43
 55  \w     37.00  63.00   1.00   12.50    --   68.00  76.00   3.17   26
 56  \w     46.00  73.00   1.00   12.50    --   68.00  71.00  22.87   27
 57  \w     37.00  64.00   1.00   12.50    --   68.00  77.00 -81.96   27
 58  \w     44.00  69.00   1.00   12.50    --   68.00  64.00 112.85   25
 59  \w     37.00  64.00   1.00   12.50    --   68.00  75.00  44.34   27
 60  \w     38.00  68.00   1.00   12.50    --   68.00  75.00-142.29   30
 61  \w     46.00  94.00   1.00   12.50    --   72.00  73.00  43.72   48
 62  \w     44.00  69.00   1.00   12.50    --   72.00  73.00 152.25   25
 63  \w     41.00  82.00   1.00   12.50    --   72.00  76.00-110.40   41
 64  \w     47.00  74.00   1.00   12.50    --   72.00  67.00 -81.95   27
 65  \w     45.00  71.00   1.00   12.50    --   72.00  68.00 -56.76   26
 66  \w     85.00 142.00   1.00   12.50    --   72.00  76.00 109.20   57
 67  \w     44.00  76.00   1.00   12.50    --   72.00  71.00 -52.46   32
 68  \w     42.00  71.00   1.00   12.50    --   72.00  77.00-140.57   29
 69  \w     41.00  67.00   1.00   12.50    --   72.00  76.00 109.20   26
 70  \w     75.00 139.00   1.00   12.50    --   72.00  74.00  64.67   64
 71  \w     43.00  69.00   1.00   12.50    --   72.00  74.00  64.67   26
 72  \w    114.00 141.00   1.00   12.50    --   72.00  73.00 134.07   27
 73  \w     44.00  69.00   1.00   12.50    --   72.00  73.00 134.07   25
 74  \w     55.00  97.00   1.00   12.50    --   76.00  64.00 -18.13   42
 75  \w     48.00  73.00   1.00   12.50    --   76.00  73.00 171.60   25
 76  \w     47.00 126.00   1.00   12.50    --   76.00  74.00-170.57   79
 77  \w     48.00  87.00   1.00   12.50    --   80.00  77.00 -58.61   39
 78  \w     49.00  75.00   1.00   12.50    --   80.00  75.00 103.73   26
 79  \w     48.00  91.00   1.00   12.50    --   80.00  77.00-139.43   43
 80  \w     56.00  81.00   1.00   12.50    --   80.00  66.00  45.49   25
 81  \w     68.00 132.00   1.00   25.00    --   84.00  61.00  43.53   64
 82  \w     57.00  83.00   1.00   25.00    --   84.00  68.00 -33.63   26
 83  \w     57.00  84.00   1.00   25.00    --   84.00  71.00   2.45   27
 84  \w    118.00 153.00   1.00   25.00    --   84.00  77.00  82.24   35
 85  \w     52.00  78.00   1.00   25.00    --   84.00  77.00  82.24   26
 86  \w     60.00  95.00   1.00   25.00    --   88.00  70.00 -82.40   35
 87  \w     61.00 107.00   1.00   25.00    --   88.00  69.00-131.56   46
 88  \w     59.00  88.00   1.00   25.00    --   88.00  72.00 108.30   29
 89  \w     56.00  83.00   1.00   25.00    --   88.00  77.00 -82.53   27
 90  \w     63.00  88.00   1.00   25.00    --   88.00  66.00 157.93   25
 91  \w     61.00 127.00   1.00   25.00    --   88.00  68.00  23.70   66
 92  \w     60.00  85.00   1.00   25.00    --   88.00  73.00 -97.33   25
 93  \w     63.00 107.00   1.00   25.00    --   88.00  68.00 -35.79   44
 94  \w     67.00 101.00   1.00   25.00    --   92.00  69.00 -62.90   34
 95  \w     70.00  95.00   1.00   25.00    --   92.00  44.00 -86.93   25
 96  \w     60.00  86.00   1.00   25.00    --   92.00  77.00-179.63   26
 97  \w     66.00  92.00   1.00   25.00    --   92.00  67.00 -10.92   26
 98  \w     69.00 133.00   1.00   25.00    --   92.00  62.00 178.48   64
 99  \w    110.00 171.00   1.00   25.00    --  100.00  75.00  63.61   61
100  \w     70.00  95.00   1.00   25.00    --  100.00  75.00  63.61   25
101  \w     78.00 128.00   1.00   25.00    --  100.00  56.00 164.82   50
102  \w     77.00 146.00   1.00   25.00    --  100.00  45.00 -61.76   69
103  \w     72.00 114.00   1.00   25.00    --  100.00  72.00  -1.46   42
104  \w     83.00 166.00   1.00   25.00    --  108.00  64.00-120.00   83
105  \w     48.00 110.00   1.00   25.00    --  108.00-111.00-180.00   62
106  \w     77.00 102.00   1.00   25.00    --  108.00  77.00 150.00   25
107  \w     46.00 132.00   1.00   25.00    --  108.00 -64.00-120.00   86
108  \w     83.00 176.00   1.00   25.00    --  108.00  64.00  30.00   93
109  \w     84.00 112.00   1.00   25.00    --  108.00  64.00 -60.00   28
110  \w     83.00 176.00   1.00   25.00    --  108.00  64.00 -90.00   93
111  \w     76.00 178.00   1.00   25.00    --  108.00  77.00 -30.00  102
112  \w     81.00 111.00   1.00   25.00    --  108.00-111.00  90.00   30
113  \w     38.00  68.00   1.00   25.00    --  108.00-111.00  90.00   30
114  \w    110.00 170.00   1.00   25.00    --  108.00  77.00  90.00   60
115  \w     77.00 104.00   1.00   25.00    --  108.00  77.00  90.00   27
116  \w     77.00 102.00   1.00   25.00    --  108.00  77.00  60.00   25
117  \w     76.00 102.00   1.00   25.00    --  108.00  77.00-150.00   26
118  \w     80.00 157.00   1.00   25.00    --  108.00  77.00   0.00   77
119  \w    133.00 173.00   1.00   25.00    --  108.00  77.00 120.00   40
120  \w     76.00 103.00   1.00   25.00    --  108.00  77.00 120.00   27
121  \w     78.00 167.00   1.00   25.00    --  108.00  77.00 -60.00   89
122  \w     61.00 110.00   1.00   25.00    --  108.00-111.00-120.00   49
123  \w    124.00 154.00   1.00   25.00    --  108.00  77.00-180.00   30
124  \w     76.00 102.00   1.00   25.00    --  108.00  77.00-180.00   26
125  \w     83.00 120.00   1.00   25.00    --  108.00  64.00  90.00   37
126  \w     76.00 102.00   1.00   25.00    --  108.00  77.00-120.00   26
127  \w     76.00 102.00   1.00   25.00    --  108.00  77.00 -90.00   26
128  \w     84.00 175.00   1.00   25.00    --  108.00  64.00-150.00   91
129  \w     35.00  98.00   1.00   25.00    --  108.00 -92.00  30.00   63
130  \w     76.00 102.00   1.00   25.00    --  108.00  77.00  30.00   26
131  \w     83.00 175.00   1.00   25.00    --  108.00  64.00 120.00   92
132  \w    142.00 169.00   1.00   25.00    --  108.00 111.00 -60.00   27
133  \w    131.00 169.00   1.00   25.00    --  108.00 111.00-150.00   38
134  \w     36.00 104.00   1.00   25.00    --  108.00 -92.00-120.00   68
135  \w     35.00  81.00   1.00   25.00    --  108.00 -92.00 120.00   46
136  \w     72.00 109.00   1.00   25.00    --  108.00-111.00   0.00   37
137  \w    131.00 165.00   1.00   25.00    --  108.00  64.00  60.00   34
138  \w     83.00 130.00   1.00   25.00    --  108.00  64.00  60.00   47
139  \w     86.00 113.00   1.00   25.00    --  108.00  64.00   0.00   27
140  \w     84.00 178.00   1.00   25.00    --  108.00  74.00 160.04   94
;
_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      0.0851504000
_diffrn_orient_matrix_UB_12      -0.0019593000
_diffrn_orient_matrix_UB_13      0.0533800000
_diffrn_orient_matrix_UB_21      -0.0036200000
_diffrn_orient_matrix_UB_22      -0.0944730000
_diffrn_orient_matrix_UB_23      0.0353901000
_diffrn_orient_matrix_UB_31      0.0739661000
_diffrn_orient_matrix_UB_32      -0.0479260000
_diffrn_orient_matrix_UB_33      -0.0784304000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0745
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            81309
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.975
_diffrn_reflns_theta_min         2.904
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.320
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.773
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (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            'dark red'
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1186
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.083
_platon_squeeze_details
'see: P. v. d. Sluis, A. L. Spek,  Acta Cryst. 1990, A46, 194.'
_refine_diff_density_max         0.598
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     669
_refine_ls_number_reflns         12018
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1015
_refine_ls_R_factor_gt           0.0627
_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^)+(0.0972P)^2^+1.0263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1646
_refine_ls_wR_factor_ref         0.1889
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7843
_reflns_number_total             12018
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00978_si_005.cif
_cod_data_source_block           ro_jd1_sq
_cod_original_cell_volume        3170.96(19)
_cod_database_code               4518621
_audit_block_refno               3706
_audit_block_usercomment         'JSD_031 irregular dark red'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Shared sites
{N4A, C17B}
{N4B, C17A}
3. Restrained distances
 C11-H11 \\sim C12-H12
 with sigma of 0.02
 C43-H43 \\sim C45-H45
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(N4A) = Uanis(C17B)
Uanis(N4B) = Uanis(C17A)
5. Rigid body (RIGU) restrains
 N6, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C7, C8, C9} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C14, C15, C16}
{N5, C48, C49, C50, C51} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N6, C53, C54, C55, C56}
7. Others
 Sof(N4B)=Sof(C17B)=Sof(H17B)=1-FVAR(1)
 Sof(N4A)=Sof(C17A)=Sof(H17A)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C7(H7), C14(H14), C23(H23), C30(H30), C35(H35), C37(H37), C40(H40)
8.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), C48(H48A,H48B), C50(H50A,H50B), C53(H53A,H53B),
 C55(H55A,H55B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B)
8.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C26(H26), C27(H27), C28(H28), C17A(H17A), C17B(H17B)
8.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), C49(H49A,H49B,H49C), C51(H51A,
 H51B,H51C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C81(H81A,H81B,H81C),
 C85(H85A,H85B,H85C)
;
_shelx_hkl_checksum              18035
_shelx_fab_checksum              13418
_platon_squeeze_void_probe_radius 1.20
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.276
_oxdiff_exptl_absorpt_empirical_full_min 0.723
_shelx_res_checksum              76558
_cell_oxdiff_length_a            14.3281(6)
_cell_oxdiff_length_b            15.1547(5)
_cell_oxdiff_length_c            15.3273(4)
_cell_oxdiff_angle_alpha         89.690(2)
_cell_oxdiff_angle_beta          83.236(3)
_cell_oxdiff_angle_gamma         73.710(3)
_cell_oxdiff_volume              3170.96(19)
_cell_oxdiff_measurement_reflns_used 12266