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_4517699
_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         'C42 H49 Ir P2 Si'
_chemical_formula_sum            'C42 H49 Ir P2 Si'
_chemical_formula_weight         836.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.1277(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.88006(7)
_cell_length_b                   21.74657(12)
_cell_length_c                   14.12314(9)
_cell_measurement_reflns_used    29456
_cell_measurement_temperature    99.97(10)
_cell_measurement_theta_max      73.3070
_cell_measurement_theta_min      3.7380
_cell_volume                     3620.52(4)
_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      99.97(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    -54.00  30.00   1.00    1.00    --  -37.09  57.00 -90.00   84
  2  \w    -56.00  32.00   1.00    1.00    --  -37.09  38.00 -90.00   88
  3  \w   -108.00  -8.00   1.00    1.00    --  -37.09 -19.00  90.00  100
  4  \w     23.00  90.00   1.00    1.00    --   37.09-125.00 -30.00   67
  5  \w      1.00  76.00   1.00    1.00    --   37.09 -99.00 -30.00   75
  6  \w    -32.00  56.00   1.00    1.00    --   37.09 -38.00   0.00   88
  7  \w    -30.00  54.00   1.00    1.00    --   37.09 -57.00  30.00   84
  8  \w     42.00 109.00   1.00    2.83    --  111.00 -94.00-120.00   67
  9  \w     93.00 178.00   1.00    2.83    --  111.00  61.00 -30.00   85
 10  \w    100.00 178.00   1.00    2.83    --  111.00 111.00 -60.00   78
 11  \w    100.00 178.00   1.00    2.83    --  111.00 111.00  90.00   78
 12  \w    100.00 178.00   1.00    2.83    --  111.00 111.00-120.00   78
 13  \w     42.00 109.00   1.00    2.83    --  111.00 -94.00 150.00   67
 14  \w     41.00 132.00   1.00    2.83    --  111.00 -30.00 -60.00   91
 15  \w     43.00 128.00   1.00    2.83    --  111.00 -45.00-150.00   85
 16  \w     44.00 129.00   1.00    2.83    --  111.00 -61.00-180.00   85
 17  \w     94.00 178.00   1.00    2.83    --  111.00  45.00 -90.00   84
 18  \w   -105.00 -10.00   1.00    1.00    --  -37.09 -77.00-120.00   95
 19  \w    -54.00  30.00   1.00    1.00    --  -37.09  57.00-180.00   84
 20  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00 -60.00   84
 21  \w    -90.00  -2.00   1.00    1.00    --  -37.09 125.00  60.00   88
 22  \w   -105.00 -10.00   1.00    1.00    --  -37.09 -77.00 120.00   95
 23  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00  30.00   84
 24  \w     73.00 178.00   1.00    2.83    --  111.00  15.00  90.00  105
 25  \w     94.00 170.00   1.00    2.83    --  111.00  45.00 -60.00   76
 26  \w     84.00 178.00   1.00    2.83    --  111.00  77.00-150.00   94
 27  \w     94.00 178.00   1.00    2.83    --  111.00  45.00 120.00   84
 28  \w     90.00 178.00   1.00    2.83    --  111.00  30.00  30.00   88
 29  \w     42.00 109.00   1.00    2.83    --  111.00 -94.00  30.00   67
 30  \w     73.00 178.00   1.00    2.83    --  111.00  15.00-150.00  105
;
_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      0.0986111000
_diffrn_orient_matrix_UB_12      0.0026895000
_diffrn_orient_matrix_UB_13      -0.0612363000
_diffrn_orient_matrix_UB_21      0.0388023000
_diffrn_orient_matrix_UB_22      -0.0644906000
_diffrn_orient_matrix_UB_23      0.0356420000
_diffrn_orient_matrix_UB_31      -0.0765390000
_diffrn_orient_matrix_UB_32      -0.0292273000
_diffrn_orient_matrix_UB_33      -0.0839703000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            42723
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.483
_diffrn_reflns_theta_min         3.752
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.500
_exptl_absorpt_correction_T_max  0.938
_exptl_absorpt_correction_T_min  0.397
_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    1.534
_exptl_crystal_description       block
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.131
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.895
_refine_diff_density_min         -0.823
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         7235
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0195
_refine_ls_R_factor_gt           0.0188
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0211P)^2^+3.9820P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0462
_refine_ls_wR_factor_ref         0.0465
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7031
_reflns_number_total             7235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           20a
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517699
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C42H49IrP2Si
_reflns_odcompleteness_completeness 99.99
_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. Restrained distances
 Ir1-H1 \\sim Ir1-H \\sim Ir1-HB \\sim Ir1-HA
 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C39(H39A,H39B), C41(H41A,H41B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
3.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              7001
_shelx_hkl_checksum              3333
_olex2_date_sample_data_collection 2019-02-05
_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 1.507
_oxdiff_exptl_absorpt_empirical_full_min 0.778