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_4517696
_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         'C25 H44 O3'
_chemical_formula_sum            'C25 H44 O3'
_chemical_formula_weight         392.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 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                 95.6028(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.21766(11)
_cell_length_b                   7.39922(9)
_cell_length_c                   12.74257(13)
_cell_measurement_reflns_used    8966
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      73.0130
_cell_measurement_theta_min      3.4650
_cell_volume                     1146.44(2)
_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      99.98(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 0.993
_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   -104.00 -20.00   1.00    2.00    --  -37.09 -57.00   0.00   84
  2  \w    -56.00  32.00   1.00    2.00    --  -37.09  38.00 -90.00   88
  3  \w    -64.00  30.00   1.00    2.00    --  -37.09  77.00-150.00   94
  4  \w   -104.00 -20.00   1.00    2.00    --  -37.09 -57.00-150.00   84
  5  \w   -106.00 -18.00   1.00    2.00    --  -37.09 -38.00 -90.00   88
  6  \w    -54.00  30.00   1.00    2.00    --  -37.09  57.00 -90.00   84
  7  \w    -66.00  34.00   1.00    2.00    --  -37.09  19.00-180.00  100
  8  \w   -104.00 -20.00   1.00    2.00    --  -37.09 -57.00 -90.00   84
  9  \w    -66.00  34.00   1.00    2.00    --  -37.09  19.00  90.00  100
 10  \w     20.00 104.00   1.00    2.00    --   37.09  57.00-180.00   84
 11  \w      8.00 108.00   1.00    2.00    --   37.09  19.00 150.00  100
 12  \w     18.00 106.00   1.00    2.00    --   37.09  38.00-120.00   88
 13  \w     43.00 139.00   1.00    8.00    --  111.00 -80.00 134.97   96
 14  \w     73.00 178.00   1.00    8.00    --  111.00  15.00 -30.00  105
 15  \w     84.00 178.00   1.00    8.00    --  111.00  77.00 -90.00   94
 16  \w     90.00 178.00   1.00    8.00    --  111.00  30.00 -30.00   88
 17  \w     90.00 178.00   1.00    8.00    --  111.00  30.00-120.00   88
 18  \w     93.00 178.00   1.00    8.00    --  111.00  61.00 -90.00   85
 19  \w     93.00 178.00   1.00    8.00    --  111.00  61.00-180.00   85
 20  \w     94.00 178.00   1.00    8.00    --  111.00  45.00 -30.00   84
 21  \w     41.00 132.00   1.00    8.00    --  111.00 -30.00-180.00   91
 22  \w     84.00 178.00   1.00    8.00    --  111.00  77.00-150.00   94
 23  \w     94.00 178.00   1.00    8.00    --  111.00  45.00-180.00   84
 24  \w     93.00 127.00   1.00    8.00    --  111.00  61.00-150.00   34
 25  \w    147.00 178.00   1.00    8.00    --  111.00  45.00   0.00   31
 26  \w     74.00 107.00   1.00    8.00    --  111.00  15.00-120.00   33
 27  \w    132.00 178.00   1.00    8.00    --  111.00  77.00-120.00   46
 28  \w     84.00 113.00   1.00    8.00    --  111.00  77.00 -60.00   29
 29  \w     84.00 111.00   1.00    8.00    --  111.00  77.00-120.00   27
 30  \w     84.00 111.00   1.00    8.00    --  111.00  77.00-180.00   27
 31  \w     90.00 178.00   1.00    8.00    --  111.00  30.00  60.00   88
 32  \w     93.00 120.00   1.00    8.00    --  111.00  61.00-120.00   27
 33  \w    123.00 178.00   1.00    8.00    --  111.00  61.00 -60.00   55
 34  \w     90.00 120.00   1.00    8.00    --  111.00  30.00 -90.00   30
 35  \w     95.00 131.00   1.00    8.00    --  111.00  45.00-150.00   36
 36  \w     98.00 125.00   1.00    8.00    --  111.00  45.00-120.00   27
 37  \w     97.00 149.00   1.00    8.00    --  111.00  45.00 -60.00   52
 38  \w     49.00 109.00   1.00    8.00    --  111.00 -61.00 150.00   60
 39  \w     43.00  71.00   1.00    8.00    --  111.00 -77.00 -90.00   28
 40  \w    -33.00  -8.00   1.00    2.00    --  -37.09 -19.00 120.00   25
 41  \w     29.00  55.00   1.00    2.00    --   37.09  57.00-150.00   26
 42  \w     94.00 120.00   1.00    8.00    --  111.00  45.00 -90.00   26
 43  \w     93.00 119.00   1.00    8.00    --  111.00  61.00 -60.00   26
 44  \w     94.00 119.00   1.00    8.00    --  111.00  45.00 -60.00   25
;
_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      -0.1259191000
_diffrn_orient_matrix_UB_12      0.0169382000
_diffrn_orient_matrix_UB_13      -0.0214324000
_diffrn_orient_matrix_UB_21      0.0137611000
_diffrn_orient_matrix_UB_22      0.0943461000
_diffrn_orient_matrix_UB_23      -0.1056692000
_diffrn_orient_matrix_UB_31      -0.0045433000
_diffrn_orient_matrix_UB_32      -0.1848005000
_diffrn_orient_matrix_UB_33      -0.0558799000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15372
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.259
_diffrn_reflns_theta_min         3.485
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.556
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.813
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.137
_exptl_crystal_description       needle
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.269
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1663 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         4287
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0321
_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^)+(0.0455P)^2^+0.1275P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0807
_refine_ls_wR_factor_ref         0.0828
_reflns_Friedel_coverage         0.736
_reflns_Friedel_fraction_full    0.882
_reflns_Friedel_fraction_max     0.859
_reflns_number_gt                4069
_reflns_number_total             4287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           16a
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517696
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C25H44O3
_reflns_odcompleteness_completeness 100.00
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3A), C5(H5), C8(H8), C9(H9), C12(H12), C14(H14), C17(H17), C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C11(H11A,
 H11B), C15(H15A,H15B), C16(H16A,H16B), C22(H22A,H22B), C23(H23A,H23B),
 C24(H24A,H24B)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C00S(H00A,H00B,
 H00C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3(H3)
;
_shelx_res_checksum              75048
_shelx_hkl_checksum              37300
_olex2_date_sample_data_collection 2019-08-09
_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 1.191
_oxdiff_exptl_absorpt_empirical_full_min 0.839