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_4517694
_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 O2'
_chemical_formula_sum            'C25 H44 O2'
_chemical_formula_weight         376.60
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-19
_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            8
_cell_length_a                   42.4084(4)
_cell_length_b                   13.60510(10)
_cell_length_c                   7.65680(10)
_cell_measurement_reflns_used    19711
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.2550
_cell_measurement_theta_min      3.3880
_cell_volume                     4417.75(8)
_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      100.00(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 0.995
_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  29.00   0.75    8.00    --  -37.09  77.00-180.00  124
  2  \w    -54.00  30.00   0.75    8.00    --  -37.09  57.00 150.00  112
  3  \w    -56.00  31.00   0.75    8.00    --  -37.09  38.00 120.00  116
  4  \w    -54.00  30.00   0.75    8.00    --  -37.09  57.00 -60.00  112
  5  \w    -32.00  55.00   0.75    8.00    --   37.09 -38.00  60.00  116
  6  \w    -32.00  55.00   0.75    8.00    --   37.09 -38.00-180.00  116
  7  \w     93.00 177.00   0.75   24.00    --  111.00  61.00-120.00  112
  8  \w     44.00 128.00   0.75   24.00    --  111.00 -61.00 120.00  112
  9  \w     41.00 131.00   0.75   24.00    --  111.00 -30.00-150.00  120
 10  \w     94.00 178.00   0.75   24.00    --  111.00  45.00-180.00  112
 11  \w     44.00 128.00   0.75   24.00    --  111.00 -61.00  60.00  112
 12  \w     84.00 177.00   0.75   24.00    --  111.00  77.00-150.00  124
 13  \w     41.00 131.00   0.75   24.00    --  111.00 -30.00 150.00  120
 14  \w     43.00 127.00   0.75   24.00    --  111.00 -45.00   0.00  112
 15  \w     41.00 131.00   0.75   24.00    --  111.00 -30.00   0.00  120
 16  \w   -104.00 -16.25   0.75    8.00    --  -37.09 -68.00  27.00  117
 17  \w    -54.00  30.00   0.75    8.00    --  -37.09  57.00  30.00  112
 18  \w   -104.00 -20.00   0.75    8.00    --  -37.09 -57.00 150.00  112
 19  \w   -104.00 -20.00   0.75    8.00    --  -37.09 -57.00  90.00  112
 20  \w   -105.00 -11.25   0.75    8.00    --  -37.09 -77.00 -90.00  125
 21  \w     43.00 136.75   0.75   24.00    --  111.00 -77.00 -90.00  125
 22  \w     73.00 178.00   0.75   24.00    --  111.00  15.00  30.00  140
 23  \w     90.00 115.50   0.75   24.00    --  111.00  30.00 -60.00   34
 24  \w     73.00 178.00   0.75   24.00    --  111.00  15.00 120.00  140
;
_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      0.0081481000
_diffrn_orient_matrix_UB_12      -0.0056752000
_diffrn_orient_matrix_UB_13      -0.1958664000
_diffrn_orient_matrix_UB_21      0.0229093000
_diffrn_orient_matrix_UB_22      0.0870463000
_diffrn_orient_matrix_UB_23      0.0212755000
_diffrn_orient_matrix_UB_31      0.0269823000
_diffrn_orient_matrix_UB_32      -0.0721866000
_diffrn_orient_matrix_UB_33      0.0410824000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            42891
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.422
_diffrn_reflns_theta_min         3.412
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.522
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.894
_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    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.046
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.128
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 3448 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     555
_refine_ls_number_reflns         8833
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0480P)^2^+0.5624P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0857
_refine_ls_wR_factor_ref         0.0871
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                8411
_reflns_number_total             8833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           17a
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517694
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C28H42O2
_reflns_odcompleteness_completeness 99.96
_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. Others
 Sof(O1)=Sof(H1)=Sof(H20)=Sof(C22)=Sof(H22C)=Sof(H22D)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(C24)=Sof(H24C)=Sof(H24D)=1-FVAR(1)
 Sof(H20A)=Sof(O1A)=Sof(H1AA)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C23A)=
 Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24A)=Sof(H24B)=FVAR(1)
 Sof(H22G)=Sof(H22H)=Sof(H24G)=Sof(H24H)=Sof(O1C)=Sof(H1C)=Sof(C23C)=Sof(H23E)=
 Sof(H23F)=1-FVAR(2)
 Sof(O1B)=Sof(H1BC)=Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(H23G)=Sof(H23H)=
 Sof(H24E)=Sof(H24F)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C9(H9), C14(H14), C17(H17), C20(H20A), C20(H20),
 C5B(H5B), C7B(H7B), C8B(H8B), C9B(H9B), C14B(H14B), C17B(H17B), C20B(H20B)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C11(H11A,
 H11B), C12(H12A,H12B), C15(H15A,H15B), C16(H16A,H16B), C22(H22C,H22D),
 C23(H23A,H23B), C24(H24C,H24D), C22A(H22A,H22B), C23A(H23C,H23D), C24A(H24A,
 H24B), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB),
 C6B(H6BA,H6BB), C11B(H11C,H11D), C12B(H12C,H12D), C15B(H15C,H15D), C16B(H16C,
 H16D), C22B(H22G,H22H), C22B(H22E,H22F), C23B(H23G,H23H), C24B(H24G,H24H),
 C24B(H24E,H24F), C23C(H23E,H23F)
3.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C25(H25A,H25B,
 H25C), C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F), C21B(H21D,H21E,H21F),
 C25B(H25D,H25E,H25F)
3.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1A(H1AA), O1B(H1BC), O1C(H1C)
;
_shelx_res_checksum              48186
_shelx_hkl_checksum              49713
_olex2_date_sample_data_collection 2019-08-16
_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 1.398
_oxdiff_exptl_absorpt_empirical_full_min 0.886