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_4517700
_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         '2(C24 H11.5 F18 Ir0.5 P)'
_chemical_formula_sum            'C48 H23 F36 Ir P2'
_chemical_formula_weight         1537.80
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                64.281(3)
_cell_angle_beta                 83.752(2)
_cell_angle_gamma                70.114(3)
_cell_formula_units_Z            2
_cell_length_a                   12.3828(3)
_cell_length_b                   15.2107(5)
_cell_length_c                   16.6665(5)
_cell_measurement_reflns_used    13197
_cell_measurement_temperature    100.1(6)
_cell_measurement_theta_max      72.5860
_cell_measurement_theta_min      4.1650
_cell_volume                     2656.74(16)
_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      100.1(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.966
_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   -105.00 -10.00   1.00    7.50    --  -37.09 -77.00 120.00   95
  2  \w    -54.00  30.00   1.00    7.50    --  -37.09  57.00   0.00   84
  3  \w   -106.00 -18.00   1.00    7.50    --  -37.09 -38.00 120.00   88
  4  \w    -32.00  30.00   1.00    7.50    --  -37.09  77.00-120.00   62
  5  \w    -47.00 -10.00   1.00    7.50    --  -37.09 -77.00   0.00   37
  6  \w    -46.00 -11.00   1.00    7.50    --  -37.09 -77.00-120.00   35
  7  \w    -21.00  25.00   1.00    7.50    --  -37.09  77.00 120.00   46
  8  \w    -91.00 -60.00   1.00    7.50    --  -37.09 -77.00-120.00   31
  9  \w   -104.00 -10.00   1.00    7.50    --  -37.09 -77.00-150.00   94
 10  \w    -59.00 -33.00   1.00    7.50    --  -37.09  69.00-142.00   26
 11  \w     27.00  58.00   1.00    7.50    --   37.09 -77.00 -60.00   31
 12  \w     16.00  42.00   1.00    7.50    --   37.09  77.00  90.00   26
 13  \w    -27.00  48.00   1.00    7.50    --   37.09 -38.00 -60.00   75
 14  \w      5.00  65.00   1.00    7.50    --   37.09 -80.00 103.95   60
 15  \w     11.00  99.00   1.00    7.50    --   37.09  77.00  30.00   88
 16  \w     60.00  86.00   1.00    7.50    --   37.09  57.00  60.00   26
 17  \w     56.00  82.00   1.00    7.50    --   37.09  77.00  90.00   26
 18  \w     92.00 178.00   1.00   30.00    --  111.00  30.00  90.00   86
 19  \w     55.00 128.00   1.00   30.00    --  111.00 -45.00 150.00   73
 20  \w     73.00 100.00   1.00   30.00    --  111.00 -80.00  -8.63   27
 21  \w    125.00 151.00   1.00   30.00    --  111.00   0.00  60.00   26
 22  \w     51.00 118.00   1.00   30.00    --  111.00 -80.00   6.17   67
 23  \w     69.00 139.00   1.00   30.00    --  111.00 -80.00 -88.44   70
 24  \w     49.00 128.00   1.00   30.00    --  111.00 -45.00   0.00   79
 25  \w     97.00 177.00   1.00   30.00    --  111.00  61.00   0.00   80
 26  \w     46.00  97.00   1.00   30.00    --  111.00   0.00  60.00   51
 27  \w     46.00 117.00   1.00   30.00    --  111.00 -45.00-120.00   71
 28  \w     68.00 111.00   1.00   30.00    --  111.00 -80.00-152.43   43
 29  \w     84.00 152.00   1.00   30.00    --  111.00  77.00  30.00   68
 30  \w     58.00 131.00   1.00   30.00    --  111.00 -30.00  60.00   73
 31  \w     71.00  98.00   1.00   30.00    --  111.00 -80.00 -22.69   27
 32  \w     71.00 103.00   1.00   30.00    --  111.00 -80.00 113.89   32
 33  \w     44.00 101.00   1.00   30.00    --  111.00 -80.00 167.81   57
 34  \w     59.00 107.00   1.00   30.00    --  111.00 -80.00  82.25   48
 35  \w     10.00  36.00   1.00    7.50    --   37.09  77.00 -30.00   26
 36  \w    -30.00  -4.00   1.00    7.50    --   37.09 -38.00 -90.00   26
 37  \w      9.00  34.00   1.00    7.50    --   37.09  80.00 -19.10   25
 38  \w     56.00  82.00   1.00    7.50    --   37.09  57.00 -60.00   26
 39  \w     71.00  97.00   1.00   30.00    --  111.00 -78.00 -44.03   26
 40  \w    124.00 149.00   1.00   30.00    --  111.00 -15.00 150.00   25
 41  \w     92.00 118.00   1.00   30.00    --  111.00 -15.00 150.00   26
 42  \w     81.00 127.00   1.00   30.00    --  111.00 -80.00  52.30   46
 43  \w    -54.00  30.00   1.00    7.50    --  -37.09  57.00  90.00   84
 44  \w   -104.00 -20.00   1.00    7.50    --  -37.09 -57.00 120.00   84
 45  \w   -104.00 -20.00   1.00    7.50    --  -37.09 -57.00 -90.00   84
 46  \w    -64.00  30.00   1.00    7.50    --  -37.09  77.00  30.00   94
 47  \w   -106.00 -18.00   1.00    7.50    --  -37.09 -38.00 -60.00   88
 48  \w    -30.00  64.00   1.00    7.50    --   37.09 -77.00-150.00   94
 49  \w     20.00  81.00   1.00    7.50    --   37.09  57.00   0.00   61
;
_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      0.0656885000
_diffrn_orient_matrix_UB_12      -0.0385669000
_diffrn_orient_matrix_UB_13      -0.0687218000
_diffrn_orient_matrix_UB_21      -0.0467119000
_diffrn_orient_matrix_UB_22      -0.0914523000
_diffrn_orient_matrix_UB_23      0.0384134000
_diffrn_orient_matrix_UB_31      -0.1050862000
_diffrn_orient_matrix_UB_32      0.0655814000
_diffrn_orient_matrix_UB_33      -0.0659573000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0567
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31423
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.388
_diffrn_reflns_theta_min         3.413
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.957
_exptl_absorpt_correction_T_max  0.983
_exptl_absorpt_correction_T_min  0.706
_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    1.922
_exptl_crystal_description       plate
_exptl_crystal_F_000             1484
_exptl_crystal_recrystallization_method 'From diisopropyl ether'
_exptl_crystal_size_max          0.058
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.006
_refine_diff_density_max         1.733
_refine_diff_density_min         -1.212
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     929
_refine_ls_number_reflns         10332
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0605
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0460P)^2^+4.5610P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7960
_reflns_number_total             10332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           21
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517700
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C49H23F36IrP2
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.688
_reflns_odcompleteness_completeness 98.78
_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 1.7 times of:
  All Ir(H,H,H,H,H) groups
2. Restrained distances
 HC-H
 -1.7 with sigma of 0.01
 H-HA
 -1.7 with sigma of 0.01
 HB-HD
 -1.7 with sigma of 0.01
 HD-HC
 -1.7 with sigma of 0.01
 HA-HB
 -1.7 with sigma of 0.01
 Ir1-HB = Ir1-HA = Ir1-H = Ir1-HC = Ir1-HD
 1.43 with sigma of 0.01
 HE-HI
 -1.7 with sigma of 0.01
 HI-HF
 -1.7 with sigma of 0.01
 HF-HG
 -1.7 with sigma of 0.01
 HG-HH
 -1.7 with sigma of 0.01
 Ir1A-HF = Ir1A-HE = Ir1A-HH = Ir1A-HI = Ir1A-HG
 1.43 with sigma of 0.01
 P1-H \\sim P1-HA \\sim P1-HB \\sim P1-HC \\sim P1-HD
 with sigma of 0.02
 P1A-HE \\sim P1A-HF \\sim P1A-HG \\sim P1A-HH \\sim P1A-HI
 with sigma of 0.02
3. Restrained planarity
 Ir1, H, HA, HB, HC, HD
 with sigma of 0.1
 Ir1A, HE, HF, HG, HH, HI
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F16 \\sim F16B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F17 \\sim F17B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F18 \\sim F18B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F9A \\sim F9B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F8A \\sim F8B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F7A \\sim F7B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F18A \\sim F18C: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F17A \\sim F17C: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
F16A \\sim F16C: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
F4 \\sim F4B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F5B \\sim F6: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F5 \\sim F6B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Others
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(1)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(2)
 Sof(F16C)=Sof(F17C)=Sof(F18C)=1-FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(3)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(4)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(4)
 Fixed Sof: H(0.5) HA(0.5) HB(0.5) HC(0.5) HD(0.5) HE(0.5) HF(0.5) HG(0.5)
 HH(0.5) HI(0.5)
6.a Fixed occupancy and ADP/Uiso:
 H, HA, HB, HC, HD, HE, HF, HG, HH, HI
6.b 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), C2A(H2A), C4A(H4A), C6A(H6A), C10A(H10A), C12A(H12A), C14A(H14A),
 C18A(H18A), C20A(H20A), C22A(H22A)
;
_shelx_res_checksum              71547
_shelx_hkl_checksum              69379
_olex2_date_sample_data_collection 2017-08-28
_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 1.606
_oxdiff_exptl_absorpt_empirical_full_min 0.776