Selectivity and Mechanism of Iridium-Catalyzed Cyclohexyl Methyl Ether Cleavage
Fast, Caleb D.; Jones, Caleb A. H.; Schley, Nathan D.; ACS Catalysis  (2020) 6450–6456; doi:10.1021/acscatal.0c01718

data_4517697
_publ_section_title
;
 Selectivity and Mechanism of Iridium-Catalyzed Cyclohexyl Methyl Ether
 Cleavage
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6450
_journal_page_last               6456
_journal_paper_doi               10.1021/acscatal.0c01718
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H42 O2'
_chemical_formula_sum            'C24 H42 O2'
_chemical_formula_weight         362.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.272(3)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   7.6128(2)
_cell_length_b                   9.7121(3)
_cell_length_c                   87.346(2)
_cell_measurement_reflns_used    13112
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.8210
_cell_measurement_theta_min      3.0170
_cell_volume                     6458.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_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    -18.00  46.00   1.00   10.00    --    8.00  79.00  86.33   64
  2  \w     -8.00  46.00   1.00   10.00    --   20.00  80.00-102.55   54
  3  \w    -63.00  30.00   1.00   10.00    --  -37.09  77.00   0.00   93
  4  \w   -106.00 -19.00   1.00   10.00    --  -37.09 -38.00  30.00   87
  5  \w    -42.00  30.00   1.00   10.00    --  -37.09  57.00-180.00   72
  6  \w     10.00  35.00   1.00   10.00    --   37.09  78.00 -22.18   25
  7  \w     12.00  42.00   1.00   10.00    --   40.00  80.00 107.54   30
  8  \w     12.00  44.00   1.00   10.00    --   40.00  80.00 -10.63   32
  9  \w     16.00  41.00   1.00   10.00    --   44.00  80.00  17.49   25
 10  \w     16.00  42.00   1.00   10.00    --   44.00  80.00-159.39   26
 11  \w     16.00  44.00   1.00   10.00    --   44.00  80.00-126.55   28
 12  \w     16.00  41.00   1.00   10.00    --   44.00  79.00 129.68   25
 13  \w     20.00  47.00   1.00   10.00    --   44.00  78.00 -94.19   27
 14  \w     20.00  45.00   1.00   10.00    --   48.00  79.00  32.63   25
 15  \w     20.00  45.00   1.00   10.00    --   48.00  80.00 154.24   25
 16  \w     20.00  45.00   1.00   10.00    --   48.00  80.00 -49.27   25
 17  \w     94.00 120.00   1.00   10.00    --   52.00  77.00 -80.36   26
 18  \w     26.00  52.00   1.00   10.00    --   52.00  77.00 -80.36   26
 19  \w     31.00  79.00   1.00   10.00    --   56.00  74.00 163.09   48
 20  \w     29.00  61.00   1.00   10.00    --   56.00  77.00 120.50   32
 21  \w     73.00 122.00   1.00   10.00    --   56.00  76.00   0.30   49
 22  \w     30.00  65.00   1.00   10.00    --   56.00  76.00   0.30   35
 23  \w     87.00 122.00   1.00   10.00    --   56.00  77.00 120.50   35
 24  \w     98.00 124.00   1.00   10.00    --   56.00  77.00  45.39   26
 25  \w     29.00  55.00   1.00   10.00    --   56.00  77.00  45.39   26
 26  \w     30.00 122.00   1.00   10.00    --   56.00  75.00-155.41   92
 27  \w     30.00  75.00   1.00   10.00    --   56.00  76.00  75.40   45
 28  \w     95.00 121.00   1.00   10.00    --   56.00  74.00-106.85   26
 29  \w     31.00  59.00   1.00   10.00    --   56.00  74.00-106.85   28
 30  \w     30.00  56.00   1.00   10.00    --   56.00  75.00 -51.68   26
 31  \w     98.00 123.00   1.00   10.00    --   56.00  74.00 163.09   25
 32  \w     34.00  99.00   1.00   10.00    --   60.00  75.00 -39.76   65
 33  \w     43.00  83.00   1.00   10.00    --   60.00  50.00 -72.32   40
 34  \w      1.00  91.00   1.00   10.00    --   68.00 -79.00  76.93   90
 35  \w     49.00  96.00   1.00   10.00    --   68.00  38.00 -37.24   47
 36  \w      0.00  96.00   1.00   10.00    --   68.00 -80.00 -83.06   96
 37  \w     52.00 100.00   1.00   10.00    --   72.00 -80.00 143.86   48
 38  \w     54.00  99.00   1.00   30.00    --   76.00  69.00 126.03   45
 39  \w     57.00  87.00   1.00   30.00    --   80.00  71.00  16.66   30
 40  \w     99.00 125.00   1.00   30.00    --   80.00  71.00  16.66   26
 41  \w     66.00  93.00   1.00   30.00    --   84.00  61.00  41.94   27
 42  \w     70.00 100.00   1.00   30.00    --   92.00  69.00-165.96   30
 43  \w    114.00 148.00   1.00   30.00    --   92.00  69.00-165.96   34
 44  \w     93.00 119.00   1.00   30.00    --  111.00  61.00-120.00   26
 45  \w     93.00 160.00   1.00   30.00    --  111.00  61.00 -60.00   67
 46  \w     84.00 173.00   1.00   30.00    --  111.00  77.00   0.00   89
 47  \w     84.00 177.00   1.00   30.00    --  111.00  77.00  60.00   93
 48  \w     93.00 162.00   1.00   30.00    --  111.00  61.00 -90.00   69
 49  \w     84.00 178.00   1.00   30.00    --  111.00  77.00 -30.00   94
 50  \w    126.00 173.00   1.00   30.00    --  111.00  77.00  30.00   47
 51  \w     84.00 113.00   1.00   30.00    --  111.00  77.00  30.00   29
 52  \w     47.00 106.00   1.00   30.00    --  111.00 -80.00-179.28   59
 53  \w     84.00 174.00   1.00   30.00    --  111.00  77.00-180.00   90
 54  \w     84.00 110.00   1.00   30.00    --  111.00  77.00 150.00   26
 55  \w    146.00 176.00   1.00   30.00    --  111.00  77.00 -60.00   30
 56  \w     84.00 110.00   1.00   30.00    --  111.00  77.00 -60.00   26
 57  \w    114.00 169.00   1.00   30.00    --  111.00  77.00-120.00   55
 58  \w     84.00 109.00   1.00   30.00    --  111.00  77.00-120.00   25
 59  \w    125.00 178.00   1.00   30.00    --  111.00  77.00 120.00   53
 60  \w     84.00 110.00   1.00   30.00    --  111.00  77.00 120.00   26
 61  \w     84.00 173.00   1.00   30.00    --  111.00  77.00  90.00   89
 62  \w     93.00 119.00   1.00   30.00    --  111.00  61.00-150.00   26
 63  \w     84.00 177.00   1.00   30.00    --  111.00  77.00-150.00   93
 64  \w     57.00 111.00   1.00   30.00    --  111.00-111.00  90.00   54
 65  \w     47.00  91.00   1.00   30.00    --  111.00 -94.00 -60.00   44
 66  \w     49.00 104.00   1.00   30.00    --  111.00 -94.00 120.00   55
 67  \w    100.00 126.00   1.00   30.00    --  111.00 111.00 120.00   26
 68  \w     83.00 120.00   1.00   30.00    --  111.00-125.00 -61.00   37
 69  \w     72.00 100.00   1.00   30.00    --  111.00 -94.00   0.00   28
 70  \w     71.00 126.00   1.00   30.00    --  111.00 -61.00 -90.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0599904000
_diffrn_orient_matrix_UB_12      -0.1458041000
_diffrn_orient_matrix_UB_13      -0.0045874000
_diffrn_orient_matrix_UB_21      -0.1640145000
_diffrn_orient_matrix_UB_22      0.0610720000
_diffrn_orient_matrix_UB_23      -0.0078619000
_diffrn_orient_matrix_UB_31      0.1023998000
_diffrn_orient_matrix_UB_32      0.0125165000
_diffrn_orient_matrix_UB_33      -0.0151065000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0501
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       103
_diffrn_reflns_limit_l_min       -108
_diffrn_reflns_number            49679
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.033
_diffrn_reflns_theta_min         3.036
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.519
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51562
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.119
_exptl_crystal_description       needle
_exptl_crystal_F_000             2424
_exptl_crystal_size_max          0.369
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.191
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 4222 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     831
_refine_ls_number_reflns         12783
_refine_ls_number_restraints     283
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0476
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0622P)^2^+1.8557P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                11010
_reflns_number_total             12783
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           15a
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        6457.9(3)
_cod_database_code               4517697
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C24H42O2
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
C9D \\sim C7D \\sim C6E \\sim C6D \\sim C5E \\sim C5D \\sim C4E \\sim C4D \\sim
C3D \\sim C3E \\sim C2D \\sim C2E \\sim C1E \\sim C1D \\sim C10E \\sim C10D
\\sim C19D \\sim C19E \\sim O1E \\sim O1D: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C19E \\sim C19D: within 1A with sigma of 0.003 and sigma for terminal atoms of
0.06
C19D \\sim C19E \\sim C10D \\sim C10E: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
3. Others
 Sof(H22E)=Sof(H22F)=Sof(O2C)=Sof(H2C)=Sof(C23C)=Sof(H23E)=Sof(H23F)=Sof(C24C)=
 Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(O2B)=Sof(H2B)=Sof(H22C)=Sof(H22D)=Sof(C23B)=Sof(H23C)=Sof(H23D)=Sof(C24B)=
 Sof(H24C)=Sof(H24D)=FVAR(1)
 Sof(O1D)=Sof(H1D)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C2D)=Sof(H2DA)=Sof(H2DB)=
 Sof(C3D)=Sof(H3D)=Sof(C4D)=Sof(H4DA)=Sof(H4DB)=Sof(C5D)=Sof(H5D)=Sof(C6D)=
 Sof(H6DA)=Sof(H6DB)=Sof(H7DC)=Sof(H7DD)=Sof(H9DA)=Sof(C10D)=Sof(C19D)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(2)
 Sof(H7DA)=Sof(H7DB)=Sof(H9D)=Sof(O1E)=Sof(H1E)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=
 Sof(C2E)=Sof(H2EA)=Sof(H2EB)=Sof(C3E)=Sof(H3E)=Sof(C4E)=Sof(H4EA)=Sof(H4EB)=
 Sof(C5E)=Sof(H5E)=Sof(C6E)=Sof(H6EA)=Sof(H6EB)=Sof(C10E)=Sof(C19E)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C3(H3), C5(H5), C8(H8), C9(H9), C14(H14), C17(H17), C20(H20), C3D(H3D),
 C5D(H5D), C8D(H8D), C9D(H9D), C9D(H9DA), C14D(H14D), C17D(H17D), C20D(H20D),
 C3E(H3E), C5E(H5E), C3B(H3B), C5B(H5B), C8B(H8B), C9B(H9B), C14B(H14B),
 C17B(H17B), C20B(H20B)
4.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1C), C2(H2A,H2E), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C11(H11E,
 H11F), C12(H12E,H12F), C15(H15E,H15F), C16(H16E,H16F), C22(H22G,H22H),
 C23(H23G,H23H), C24(H24G,H24H), C1D(H1DA,H1DB), C2D(H2DA,H2DB), C4D(H4DA,H4DB),
  C6D(H6DA,H6DB), C7D(H7DA,H7DB), C7D(H7DC,H7DD), C11D(H11A,H11B), C12D(H12A,
 H12B), C15D(H15A,H15B), C16D(H16A,H16B), C22D(H22A,H22B), C23D(H23A,H23B),
 C24D(H24A,H24B), C1E(H1EA,H1EB), C2E(H2EA,H2EB), C4E(H4EA,H4EB), C6E(H6EA,
 H6EB), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C4B(H4BA,H4BB), C6B(H6BA,H6BB),
 C7B(H7BA,H7BB), C11B(H11C,H11D), C12B(H12C,H12D), C15B(H15C,H15D), C16B(H16C,
 H16D), C22B(H22C,H22D), C22B(H22E,H22F), C23B(H23C,H23D), C24B(H24C,H24D),
 C23C(H23E,H23F), C24C(H24E,H24F)
4.c Idealised Me refined as rotating group:
 C18(H18G,H18H,H18I), C19(H19J,H19K,H19L), C21(H21G,H21H,H21I), C18D(H18A,H18B,
 H18C), C19D(H19A,H19B,H19C), C21D(H21A,H21B,H21C), C19E(H19D,H19E,H19F),
 C18B(H18D,H18E,H18F), C19B(H19G,H19H,H19I), C21B(H21D,H21E,H21F)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O1D(H1D), O2D(H2D), O1E(H1E), O1B(H1B), O2B(H2B), O2C(H2C)
;
_shelx_res_checksum              86715
_shelx_hkl_checksum              47696
_olex2_date_sample_data_collection 2019-08-13
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.377
_oxdiff_exptl_absorpt_empirical_full_min 0.534