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_4517698
_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         'C20 H28 O2'
_chemical_formula_sum            'C20 H28 O2'
_chemical_formula_weight         300.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-30
_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
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.77350(10)
_cell_length_b                   12.29960(10)
_cell_length_c                   16.91550(10)
_cell_measurement_reflns_used    6382
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.2080
_cell_measurement_theta_min      4.4350
_cell_volume                     1617.31(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 0.991
_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    -64.00  30.00   1.00    1.00    --  -37.09  77.00 120.00   94
  2  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00  30.00   84
  3  \w    -30.00  54.00   1.00    1.00    --   37.09 -57.00 -60.00   84
  4  \w     23.00  90.00   1.00    1.00    --   37.09-125.00  60.00   67
  5  \w    100.00 178.00   1.00    3.84    --  111.00 111.00-180.00   78
  6  \w     41.00 132.00   1.00    3.84    --  111.00 -30.00  90.00   91
  7  \w     42.00 109.00   1.00    3.84    --  111.00 -94.00 -90.00   67
  8  \w     41.00 116.00   1.00    3.84    --  111.00-111.00 150.00   75
  9  \w     42.00 109.00   1.00    3.84    --  111.00 -94.00   0.00   67
 10  \w     42.00 109.00   1.00    3.84    --  111.00 -94.00  30.00   67
 11  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00 120.00   84
 12  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00-150.00   84
 13  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00 -60.00   84
 14  \w     89.00 114.00   1.00    3.84    --  111.00  69.00  35.00   25
 15  \w     90.00 178.00   1.00    3.84    --  111.00  30.00 -90.00   88
 16  \w     90.00 178.00   1.00    3.84    --  111.00  30.00 120.00   88
;
_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      -0.0967373000
_diffrn_orient_matrix_UB_12      0.0844816000
_diffrn_orient_matrix_UB_13      -0.0505401000
_diffrn_orient_matrix_UB_21      0.0786496000
_diffrn_orient_matrix_UB_22      -0.0494386000
_diffrn_orient_matrix_UB_23      -0.0754757000
_diffrn_orient_matrix_UB_31      -0.1540998000
_diffrn_orient_matrix_UB_32      -0.0780787000
_diffrn_orient_matrix_UB_33      -0.0067942000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9160
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.469
_diffrn_reflns_theta_min         4.445
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.748
_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    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.067
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.173
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1262 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(9)
_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     202
_refine_ls_number_reflns         3188
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0425P)^2^+0.3203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0792
_refine_ls_wR_factor_ref         0.0804
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                3083
_reflns_number_total             3188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           19
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517698
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C20H28O2
_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
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C14(H14), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B),
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              90109
_shelx_hkl_checksum              92235
_olex2_date_sample_data_collection 2019-04-30
_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 1.116
_oxdiff_exptl_absorpt_empirical_full_min 0.879