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_4517702
_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_formula_moiety         'C24 H18 F9 P'
_chemical_formula_sum            'C24 H18 F9 P'
_chemical_formula_weight         508.35
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                62.798(3)
_cell_angle_beta                 76.382(2)
_cell_angle_gamma                76.134(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2013(3)
_cell_length_b                   11.6473(3)
_cell_length_c                   12.4438(3)
_cell_measurement_reflns_used    11031
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.0690
_cell_measurement_theta_min      4.0080
_cell_volume                     1139.24(6)
_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 0.987
_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    -64.00  30.00   1.00    1.00    --  -37.34  77.00  90.00   94
  2  \w   -105.00 -11.00   1.00    1.00    --  -37.34 -77.00  90.00   94
  3  \w   -105.00 -11.00   1.00    1.00    --  -37.34 -77.00 150.00   94
  4  \w   -105.00 -11.00   1.00    1.00    --  -37.34 -77.00   0.00   94
  5  \w    -54.00  30.00   1.00    1.00    --  -37.34  57.00 -60.00   84
  6  \w   -105.00 -21.00   1.00    1.00    --  -37.34 -57.00 150.00   84
  7  \w    -30.00  64.00   1.00    1.00    --   37.34 -77.00-150.00   94
  8  \w     18.00 106.00   1.00    1.00    --   37.34  38.00 150.00   88
  9  \w     21.00 105.00   1.00    1.00    --   37.34  57.00  60.00   84
 10  \w    -30.00  64.00   1.00    1.00    --   37.34 -77.00-120.00   94
 11  \w     21.00 105.00   1.00    1.00    --   37.34  57.00  30.00   84
 12  \w    -30.00  64.00   1.00    1.00    --   37.34 -77.00 -60.00   94
 13  \w     11.00 105.00   1.00    1.00    --   37.34  77.00 -60.00   94
 14  \w      9.00  46.00   1.00    1.00    --   37.34  80.00  55.68   37
 15  \w      8.00 109.00   1.00    1.00    --   37.34  19.00 -30.00  101
 16  \w     43.00 128.00   1.00    1.59    --  111.00 -45.00 -90.00   85
 17  \w     90.00 178.00   1.00    1.59    --  111.00  30.00 150.00   88
 18  \w     43.00 138.00   1.00    1.59    --  111.00 -78.00  85.68   95
 19  \w     41.00 132.00   1.00    1.59    --  111.00 -30.00-150.00   91
 20  \w     41.00 132.00   1.00    1.59    --  111.00 -30.00 120.00   91
 21  \w     43.00 138.00   1.00    1.59    --  111.00 -78.00 172.86   95
 22  \w     43.00 139.00   1.00    1.59    --  111.00 -80.00  42.08   96
 23  \w     43.00 128.00   1.00    1.59    --  111.00 -45.00   0.00   85
 24  \w     43.00 139.00   1.00    1.59    --  111.00 -79.00 -54.45   96
 25  \w     41.00 132.00   1.00    1.59    --  111.00 -30.00  53.00   91
 26  \w     42.00 178.00   1.00    1.59    --  111.00   0.00 -60.00  136
 27  \w     43.00 138.00   1.00    1.59    --  111.00 -77.00 -30.00   95
 28  \w     43.00 138.00   1.00    1.59    --  111.00 -78.00 145.26   95
 29  \w     43.00 139.00   1.00    1.59    --  111.00 -80.00-130.25   96
 30  \w    -64.00  30.00   1.00    1.00    --  -37.34  77.00  60.00   94
 31  \w    -64.00  30.00   1.00    1.00    --  -37.34  77.00 150.00   94
 32  \w   -105.00 -21.00   1.00    1.00    --  -37.34 -57.00-150.00   84
 33  \w   -106.00 -18.00   1.00    1.00    --  -37.34 -38.00-120.00   88
 34  \w   -105.00 -11.00   1.00    1.00    --  -37.34 -77.00 -60.00   94
 35  \w    -54.00  30.00   1.00    1.00    --  -37.34  57.00  90.00   84
 36  \w   -105.00 -11.00   1.00    1.00    --  -37.34 -77.00-150.00   94
 37  \w     21.00 105.00   1.00    1.00    --   37.34  57.00-150.00   84
 38  \w     21.00 105.00   1.00    1.00    --   37.34  57.00-180.00   84
 39  \w    -34.00  67.00   1.00    1.00    --   37.34 -19.00-180.00  101
 40  \w    -30.00  64.00   1.00    1.00    --   37.34 -77.00-180.00   94
 41  \w    -32.00 107.00   1.00    1.00    --   37.34   0.00-150.00  139
 42  \w    -30.00  54.00   1.00    1.00    --   37.34 -57.00   0.00   84
 43  \w     21.00 105.00   1.00    1.00    --   37.34  57.00   0.00   84
 44  \w     73.00 178.00   1.00    1.59    --  111.00  15.00  60.00  105
 45  \w     84.00 157.00   1.00    1.59    --  111.00  77.00-120.00   73
 46  \w     94.00 178.00   1.00    1.59    --  111.00  45.00-180.00   84
 47  \w     94.00 178.00   1.00    1.59    --  111.00  45.00  90.00   84
 48  \w     90.00 178.00   1.00    1.59    --  111.00  30.00   0.00   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      -0.1188766000
_diffrn_orient_matrix_UB_12      0.0981932000
_diffrn_orient_matrix_UB_13      0.0376728000
_diffrn_orient_matrix_UB_21      -0.1237752000
_diffrn_orient_matrix_UB_22      -0.0351435000
_diffrn_orient_matrix_UB_23      -0.0393361000
_diffrn_orient_matrix_UB_31      -0.0305730000
_diffrn_orient_matrix_UB_32      -0.1084796000
_diffrn_orient_matrix_UB_33      0.1297309000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0277
_diffrn_reflns_av_unetI/netI     0.0215
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21511
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.368
_diffrn_reflns_theta_min         4.037
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.849
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.782
_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    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             516
_exptl_crystal_recrystallization_method
'Crystallization of a neat oil (obtained from a diethyl ether solution) on standing.'
_exptl_crystal_size_max          0.209
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.059
_refine_diff_density_max         1.473
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4463
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0708
_refine_ls_R_factor_gt           0.0653
_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^)+(0.0783P)^2^+2.2013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1720
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4014
_reflns_number_total             4463
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           23
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        1139.23(6)
_cod_database_code               4517702
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C24H18F9P
_reflns_odcompleteness_completeness 98.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C10(H10), C12(H12), C14(H14), C18(H18), C20(H20),
 C22(H22)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              88429
_shelx_hkl_checksum              17961
_olex2_date_sample_data_collection 2018-12-04
_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 1.138
_oxdiff_exptl_absorpt_empirical_full_min 0.863