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_4518618
_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_absolute_configuration ad
_chemical_formula_sum            'C40 H58 Cl2 Fe N4 O'
_chemical_formula_weight         737.65
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ro_dr12
_audit_creation_date             2019-08-12
_audit_creation_method
;
encif (version 1.123)

encifer (version_id = 274361.64)

Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6226)
;
_audit_update_record
'07.12.2020 16:18:56 CET UTC+01:00  encif 1.123'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   26.4101(5)
_cell_length_b                   26.4101(5)
_cell_length_c                   10.6187(2)
_cell_measurement_reflns_used    8309
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      41.8880
_cell_measurement_theta_min      3.3500
_cell_volume                     6414.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_publication_material
'encif (Wadepohl, 2009-20); 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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -29.00  39.00   1.00   10.00    --    0.00  77.00 150.00   68
  2  \w    -69.00  19.00   1.00   10.00    --    0.00 -57.00 120.00   88
  3  \w    -20.00  68.00   1.00   10.00    --    0.00  57.00 -90.00   88
  4  \w    -21.00   7.00   1.00   10.00    --   14.00 109.00 115.29   28
  5  \w    -24.00  14.00   1.00   10.00    --   14.00 100.00 -71.60   38
  6  \w    -17.00  11.00   1.00   10.00    --   26.00 101.00 100.05   28
  7  \w      1.00  26.00   1.00   20.00    --   38.00  89.00-173.81   25
  8  \w      2.00  27.00   1.00   20.00    --   38.00  88.00  31.98   25
  9  \w     14.00  39.00   1.00   20.00    --   46.00  80.00 146.84   25
 10  \w     13.00  38.00   1.00   20.00    --   46.00  82.00 -36.46   25
 11  \w     14.00  39.00   1.00   20.00    --   46.00  80.00   0.09   25
 12  \w     14.00  39.00   1.00   20.00    --   46.00  81.00 -68.58   25
 13  \w     15.00  40.00   1.00   20.00    --   46.00  79.00-103.41   25
 14  \w     16.00  41.00   1.00   20.00    --   46.00  77.00  76.19   25
 15  \w     15.00  40.00   1.00   20.00    --   46.00  81.00  52.96   25
 16  \w     13.00  38.00   1.00   20.00    --   46.00  82.00-132.91   25
 17  \w     13.00  38.00   1.00   20.00    --   46.00  82.00 104.46   25
 18  \w     16.00  41.00   1.00   20.00    --   46.00  77.00  36.70   25
 19  \w     86.00 114.00   1.00   20.00    --   50.00  72.00 -40.94   28
 20  \w     25.00  63.00   1.00   20.00    --   50.00  72.00-170.88   38
 21  \w     23.00  57.00   1.00   20.00    --   50.00  71.00 131.55   34
 22  \w     25.00  52.00   1.00   20.00    --   50.00  72.00 -40.94   27
 23  \w     27.00  54.00   1.00   20.00    --   54.00  73.00  32.06   27
 24  \w     28.00  61.00   1.00   20.00    --   54.00  72.00   9.31   33
 25  \w     28.00  53.00   1.00   20.00    --   54.00  72.00 -74.57   25
 26  \w      6.00  95.00   1.00   20.00    --   54.00 -99.00-180.00   89
 27  \w     28.00  53.00   1.00   20.00    --   54.00  72.00 -29.30   25
 28  \w     28.00  80.00   1.00   20.00    --   54.00-125.00 120.00   52
 29  \w     30.00  57.00   1.00   20.00    --   54.00  72.00 125.56   27
 30  \w     27.00  53.00   1.00   20.00    --   54.00  72.00-122.11   26
 31  \w     26.00  53.00   1.00   20.00    --   54.00  73.00-152.20   27
 32  \w    -15.00  83.00   1.00   20.00    --   54.00 -77.00 -60.00   98
 33  \w     30.00  57.00   1.00   20.00    --   58.00  73.00 178.86   27
 34  \w     31.00  56.00   1.00   20.00    --   58.00  74.00 -93.50   25
 35  \w     35.00  74.00   1.00   20.00    --   58.00  67.00  20.22   39
 36  \w     30.00  56.00   1.00   20.00    --   58.00  74.00  63.94   26
 37  \w     32.00  59.00   1.00   20.00    --   58.00  71.00 -48.51   27
 38  \w     31.00  64.00   1.00   20.00    --   58.00  73.00  55.91   33
 39  \w    102.00 127.00   1.00   20.00    --   58.00  73.00  55.91   25
 40  \w     31.00  58.00   1.00   20.00    --   58.00  72.00 101.41   27
 41  \w     33.00  60.00   1.00   20.00    --   58.00  72.00-135.24   27
 42  \w     38.00  65.00   1.00   20.00    --   58.00  74.00 138.77   27
 43  \w     32.00  59.00   1.00   20.00    --   58.00  72.00  86.45   27
 44  \w     31.00  58.00   1.00   20.00    --   58.00  74.00 109.96   27
 45  \w     33.00 127.00   1.00   20.00    --   58.00  74.00  27.85   94
 46  \w     30.00  56.00   1.00   20.00    --   58.00  74.00-103.77   26
 47  \w     30.00  57.00   1.00   20.00    --   58.00  74.00 131.92   27
 48  \w     31.00  56.00   1.00   20.00    --   58.00  74.00 -29.07   25
 49  \w     35.00  60.00   1.00   20.00    --   62.00  74.00-166.39   25
 50  \w     38.00  65.00   1.00   20.00    --   62.00  72.00 174.63   27
 51  \w     35.00  62.00   1.00   20.00    --   62.00  72.00  39.48   27
 52  \w     38.00  65.00   1.00   20.00    --   62.00  70.00  77.32   27
 53  \w     35.00  62.00   1.00   20.00    --   62.00  72.00-135.05   27
 54  \w     43.00  73.00   1.00   20.00    --   62.00  65.00  94.29   30
 55  \w     35.00  62.00   1.00   20.00    --   62.00  72.00 -29.98   27
 56  \w     35.00  62.00   1.00   20.00    --   62.00  71.00 160.68   27
 57  \w     36.00  63.00   1.00   20.00    --   62.00  72.00 -81.27   27
 58  \w     34.00  60.00   1.00   20.00    --   62.00  74.00 132.95   26
 59  \w     38.00  79.00   1.00   20.00    --   66.00  73.00  55.80   41
 60  \w     38.00  65.00   1.00   20.00    --   66.00  74.00 -22.14   27
 61  \w     39.00  66.00   1.00   20.00    --   66.00  72.00 -62.03   27
 62  \w     38.00  65.00   1.00   20.00    --   66.00  74.00 150.18   27
 63  \w     85.00 114.00   1.00   20.00    --   66.00  68.00 -23.74   29
 64  \w     42.00  76.00   1.00   20.00    --   66.00  68.00 -23.74   34
 65  \w    111.00 136.00   1.00   20.00    --   66.00  74.00-105.77   25
 66  \w     40.00  67.00   1.00   20.00    --   66.00  73.00-131.41   27
 67  \w     46.00  73.00   1.00   20.00    --   66.00  68.00 -80.46   27
 68  \w     44.00  94.00   1.00   20.00    --   66.00  73.00 105.01   50
 69  \w     39.00  64.00   1.00   20.00    --   66.00  74.00-105.77   25
 70  \w     41.00  75.00   1.00   20.00    --   66.00  72.00 126.93   34
 71  \w     42.00  85.00   1.00   20.00    --   70.00  74.00  10.03   43
 72  \w     43.00  74.00   1.00   20.00    --   70.00  71.00 -20.18   31
 73  \w     43.00  75.00   1.00   20.00    --   70.00  74.00  88.88   32
 74  \w     46.00  80.00   1.00   20.00    --   70.00  67.00  68.91   34
 75  \w     42.00  69.00   1.00   20.00    --   70.00  74.00  -6.86   27
 76  \w     51.00  80.00   1.00   20.00    --   70.00  64.00-117.61   29
 77  \w     42.00  74.00   1.00   20.00    --   70.00  74.00  38.19   32
 78  \w     47.00  72.00   1.00   20.00    --   70.00  68.00 155.11   25
 79  \w     53.00 137.00   1.00   20.00    --   70.00  63.00-133.71   84
 80  \w     44.00  90.00   1.00   20.00    --   70.00  70.00-175.47   46
 81  \w     46.00  74.00   1.00   20.00    --   70.00  69.00-109.15   28
 82  \w     48.00  79.00   1.00   20.00    --   74.00  71.00 154.67   31
 83  \w     51.00  78.00   1.00   20.00    --   74.00  74.00-116.46   27
 84  \w     58.00 139.00   1.00   20.00    --   74.00  68.00 -88.84   81
 85  \w     52.00 100.00   1.00   20.00    --   74.00  67.00 102.97   48
 86  \w     57.00  82.00   1.00   20.00    --   74.00  62.00 -58.03   25
 87  \w     48.00  79.00   1.00   20.00    --   74.00  71.00  67.58   31
 88  \w     50.00  76.00   1.00   20.00    --   74.00  67.00 -94.29   26
 89  \w     49.00  81.00   1.00   20.00    --   74.00  69.00 -48.37   32
 90  \w     53.00  81.00   1.00   20.00    --   74.00  65.00 126.49   28
 91  \w     56.00  81.00   1.00   20.00    --   78.00  64.00 142.61   25
 92  \w     57.00  89.00   1.00   20.00    --   78.00  63.00 -50.15   32
 93  \w     53.00  78.00   1.00   20.00    --   78.00  70.00 -43.84   25
 94  \w     50.00  81.00   1.00   20.00    --   78.00  74.00 177.00   31
 95  \w     56.00  83.00   1.00   20.00    --   78.00  70.00  13.53   27
 96  \w     56.00  89.00   1.00   20.00    --   78.00  61.00  18.09   33
 97  \w     56.00 109.00   1.00   25.00    --   82.00  71.00 145.18   53
 98  \w     56.00  83.00   1.00   25.00    --   82.00  70.00   7.47   27
 99  \w     58.00  84.00   1.00   25.00    --   82.00  67.00-102.60   26
100  \w     61.00  88.00   1.00   25.00    --   82.00  58.00 133.46   27
101  \w     56.00  94.00   1.00   25.00    --   82.00  72.00 -86.64   38
102  \w     54.00  87.00   1.00   25.00    --   82.00  73.00  66.76   33
103  \w     55.00 112.00   1.00   25.00    --   82.00  74.00 -37.89   57
104  \w     54.00  87.00   1.00   25.00    --   82.00  73.00-170.40   33
105  \w     64.00 148.00   1.00   25.00    --   82.00  62.00-178.52   84
106  \w     58.00  85.00   1.00   25.00    --   82.00  69.00 -43.76   27
107  \w     67.00  97.00   1.00   25.00    --   86.00  53.00-112.95   30
108  \w     63.00  90.00   1.00   25.00    --   86.00  68.00  82.82   27
109  \w     58.00  94.00   1.00   25.00    --   86.00  74.00-158.96   36
110  \w     71.00  98.00   1.00   25.00    --   86.00  72.00 -47.27   27
111  \w     68.00 150.00   1.00   25.00    --   86.00  50.00   5.06   82
112  \w     67.00  94.00   1.00   25.00    --   86.00  72.00  -2.96   27
113  \w     63.00  89.00   1.00   25.00    --   86.00  67.00  69.03   26
114  \w     65.00 137.00   1.00   25.00    --   86.00  60.00 -60.56   72
115  \w     64.00  95.00   1.00   25.00    --   86.00  63.00  33.61   31
116  \w     68.00  95.00   1.00   25.00    --   90.00  63.00 102.35   27
117  \w     72.00 157.00   1.00   25.00    --   90.00  60.00  28.11   85
118  \w     72.00  99.00   1.00   25.00    --   90.00  59.00-113.43   27
119  \w     69.00 102.00   1.00   25.00    --   90.00  55.00 -15.20   33
120  \w     66.00 132.00   1.00   25.00    --   90.00  41.00 163.56   66
121  \w     66.00  93.00   1.00   25.00    --   94.00  73.00  41.71   27
122  \w     67.00  97.00   1.00   25.00    --   94.00  71.00-155.20   30
123  \w     67.00  94.00   1.00   25.00    --   94.00  71.00 -19.65   27
124  \w     79.00 161.00   1.00   25.00    --   94.00  67.00-146.36   82
125  \w     67.00  96.00   1.00   25.00    --   94.00  71.00 -73.53   29
126  \w     79.00 106.00   1.00   25.00    --   94.00  54.00-103.79   27
127  \w     70.00 113.00   1.00   25.00    --   98.00  74.00 139.81   43
128  \w     77.00 104.00   1.00   25.00    --   98.00  48.00 111.73   27
129  \w     73.00  99.00   1.00   25.00    --   98.00  69.00 -34.24   26
130  \w     71.00  97.00   1.00   25.00    --   98.00  71.00  64.30   26
131  \w     74.00 158.00   1.00   25.00    --   98.00  68.00 165.38   84
132  \w     71.00  98.00   1.00   25.00    --   98.00  74.00  93.19   27
133  \w     81.00 107.00   1.00   25.00    --  102.00  58.00 -51.20   26
;
_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      0.0588465000
_diffrn_orient_matrix_UB_12      0.0010437000
_diffrn_orient_matrix_UB_13      -0.0034077000
_diffrn_orient_matrix_UB_21      0.0117909000
_diffrn_orient_matrix_UB_22      0.0268163000
_diffrn_orient_matrix_UB_23      -0.1330127000
_diffrn_orient_matrix_UB_31      0.0305520000
_diffrn_orient_matrix_UB_32      0.0617569000
_diffrn_orient_matrix_UB_33      0.0578442000
_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  0.1967
_diffrn_reflns_av_unetI/netI     0.1050
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            139163
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        65.633
_diffrn_reflns_theta_max         65.633
_diffrn_reflns_theta_min         3.347
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.220
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7831
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53a (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.146
_exptl_crystal_description       needle
_exptl_crystal_F_000             2364
_exptl_crystal_size_max          0.085
_exptl_crystal_size_mid          0.028
_exptl_crystal_size_min          0.023
_platon_squeeze_details
'see: P. v. d. Sluis, A. L. Spek,  Acta Cryst. 1990, A46, 194.'
_refine_diff_density_max         0.315
_refine_diff_density_min         -0.359
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1433 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     446
_refine_ls_number_reflns         7149
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.1329
_refine_ls_R_factor_gt           0.0575
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0793P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1487
_reflns_Friedel_coverage         0.835
_reflns_Friedel_fraction_full    0.935
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                4252
_reflns_number_total             7149
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00978_si_002.cif
_cod_data_source_block           ro_dr12_sq
_cod_original_cell_volume        6414.2(3)
_cod_database_code               4518618
_audit_block_refno               3396
_audit_block_usercomment         'DAR-PE-015 needle blue-green'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     60.73
_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. Restrained distances
 C52-C53 \\sim C53-C54 \\sim C54-C55
 with sigma of 0.02
 O51-C52 \\sim O51-C55
 with sigma of 0.02
 O51-C53 \\sim O51-C54
 with sigma of 0.04
 C53-C55 \\sim C52-C54
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O51 \\sim C52 \\sim C53 \\sim C54 \\sim C55: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O51, C52, C53, C54, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C7(H7), C14(H14), C23(H23), C30(H30)
5.b Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C17(H17), C26(H26), C27(H27), C28(H28)
5.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), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_hkl_checksum              97474
_shelx_fab_checksum              38405
_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
- B-factor correction
;
_shelx_res_checksum              63809
_cell_oxdiff_measurement_reflns_used 8309