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_4517692
_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         'C56 H48 F18 Ir P2, C32 H12 B F24'
_chemical_formula_sum            'C88 H60 B F42 Ir P2'
_chemical_formula_weight         2180.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.7800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0737(2)
_cell_length_b                   23.7759(3)
_cell_length_c                   28.1916(4)
_cell_measurement_reflns_used    24300
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.2200
_cell_measurement_theta_min      3.1640
_cell_volume                     8635.7(2)
_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 0.985
_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    3.00    --  -37.50  77.00  30.00   94
  2  \w    -54.00  30.00   1.00    3.00    --  -37.50  57.00  90.00   84
  3  \w    -64.00  30.00   1.00    3.00    --  -37.50  77.00 -30.00   94
  4  \w   -105.00 -21.00   1.00    3.00    --  -37.50 -57.00-180.00   84
  5  \w    -54.00  30.00   1.00    3.00    --  -37.50  57.00-150.00   84
  6  \w     23.00  91.00   1.00    3.00    --   37.50-125.00 -30.00   68
  7  \w      1.00  76.00   1.00    3.00    --   37.50 -99.00 120.00   75
  8  \w     21.00 105.00   1.00    3.00    --   37.50  57.00   0.00   84
  9  \w      1.00  76.00   1.00    3.00    --   37.50 -99.00 -30.00   75
 10  \w     23.00  91.00   1.00    3.00    --   37.50-125.00 -60.00   68
 11  \w     19.00 107.00   1.00    3.00    --   37.50  38.00  90.00   88
 12  \w    -30.00  54.00   1.00    3.00    --   37.50 -57.00-150.00   84
 13  \w      1.00  76.00   1.00    3.00    --   37.50 -99.00  30.00   75
 14  \w     93.00 178.00   1.00   14.00    --  111.00  61.00  30.00   85
 15  \w     93.00 178.00   1.00   14.00    --  111.00  61.00 -60.00   85
 16  \w     42.00 109.00   1.00   14.00    --  111.00 -94.00  60.00   67
 17  \w     42.00 109.00   1.00   14.00    --  111.00 -94.00 -60.00   67
 18  \w     43.00 128.00   1.00   14.00    --  111.00 -45.00-150.00   85
 19  \w    112.00 148.00   1.00   14.00    --  111.00  45.00   0.00   36
 20  \w     50.00 102.00   1.00   14.00    --  111.00-111.00 -90.00   52
 21  \w     41.00 116.00   1.00   14.00    --  111.00-111.00   0.00   75
 22  \w     45.00 124.00   1.00   14.00    --  111.00 -61.00 -30.00   79
 23  \w     94.00 138.00   1.00   14.00    --  111.00  61.00  60.00   44
 24  \w     57.00 132.00   1.00   14.00    --  111.00 -30.00 -90.00   75
;
_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      0.0200465000
_diffrn_orient_matrix_UB_12      0.0638678000
_diffrn_orient_matrix_UB_13      0.0021834000
_diffrn_orient_matrix_UB_21      0.1165972000
_diffrn_orient_matrix_UB_22      -0.0108382000
_diffrn_orient_matrix_UB_23      0.0171798000
_diffrn_orient_matrix_UB_31      0.0174263000
_diffrn_orient_matrix_UB_32      -0.0008972000
_diffrn_orient_matrix_UB_33      -0.0526844000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            65028
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.348
_diffrn_reflns_theta_min         2.446
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.589
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.239
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.677
_exptl_crystal_description       plate
_exptl_crystal_F_000             4312
_exptl_crystal_recrystallization_method
'From a saturated ether/pentane solution'
_exptl_crystal_size_max          0.315
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.012
_refine_diff_density_max         1.653
_refine_diff_density_min         -1.289
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1356
_refine_ls_number_reflns         17098
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0653
_refine_ls_R_factor_gt           0.0566
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0210P)^2^+55.6157P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1239
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14944
_reflns_number_total             17098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           1e
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_database_code               4517692
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C88H60BF42IrP2
_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. Uiso/Uaniso restraints and constraints
H50 \\sim F37 \\sim F37B \\sim F38 \\sim F38B \\sim F39 \\sim F39B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
F31 \\sim F31B \\sim F32 \\sim F32B \\sim F33 \\sim F33B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(F13B)=Sof(F14B)=Sof(F15B)=Sof(H48A)=Sof(H48B)=Sof(H48C)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=Sof(H56A)=Sof(H56B)=Sof(H56C)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(2)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(3)
 Sof(F37B)=Sof(F38B)=Sof(F39B)=1-FVAR(4)
 Sof(F37)=Sof(F38)=Sof(F39)=FVAR(4)
 Sof(F31B)=Sof(F32B)=Sof(F33B)=1-FVAR(5)
 Sof(F31)=Sof(F32)=Sof(F33)=FVAR(5)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C12(H12), C14(H14), C18(H18), C20(H20), C22(H22), C26(H26),
 C28(H28), C30(H30), C34(H34), C36(H36), C38(H38), C42(H42), C44(H44), C46(H46),
  C50(H50), C52(H52), C54(H54), C58(H58), C60(H60), C62(H62), C66(H66),
 C68(H68), C70(H70), C74(H74), C76(H76), C78(H78), C82(H82), C84(H84), C86(H86)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C39(H39A,H39B,H39C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              79996
_shelx_hkl_checksum              27546
_olex2_date_sample_data_collection 2018-12-05
_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 1.197
_oxdiff_exptl_absorpt_empirical_full_min 0.835