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_4517689
_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         'C34 H38 Ir P2, C32 H12 B F24'
_chemical_formula_sum            'C66 H50 B F24 Ir P2'
_chemical_formula_weight         1564.01
_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             2018-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                107.1150(10)
_cell_angle_beta                 90.4073(8)
_cell_angle_gamma                98.3956(9)
_cell_formula_units_Z            4
_cell_length_a                   14.47472(15)
_cell_length_b                   19.2600(2)
_cell_length_c                   23.9417(3)
_cell_measurement_reflns_used    47098
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      66.2170
_cell_measurement_theta_min      3.0660
_cell_volume                     6301.75(13)
_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      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_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    -63.00  31.00   1.00    1.04    --  -36.45  77.00-180.00   94
  2  \w    -63.00  31.00   1.00    1.04    --  -36.45  77.00 -30.00   94
  3  \w   -106.00  33.00   1.00    1.04    --  -36.45   0.00-180.00  139
  4  \w    -53.00  31.00   1.00    1.04    --  -36.45  57.00  30.00   84
  5  \w    -31.00  63.00   1.00    1.04    --   36.45 -77.00  60.00   94
  6  \w     20.00 104.00   1.00    1.04    --   36.45  57.00  60.00   84
  7  \w     10.00 104.00   1.00    1.04    --   36.45  77.00 -90.00   94
  8  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00 106.93   96
  9  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00 -26.04   96
 10  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00 -78.02   96
 11  \w     75.00 166.00   1.00    4.14    --   96.52  30.00-120.00   91
 12  \w     25.00 135.00   1.00    4.14    --   96.52 -15.00-150.00  110
 13  \w     27.00 118.00   1.00    4.14    --   96.52 -30.00  60.00   91
 14  \w     78.00 163.00   1.00    4.14    --   96.52  61.00  30.00   85
 15  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00-126.44   96
 16  \w     27.00 118.00   1.00    4.14    --   96.52 -30.00 -30.00   91
 17  \w     78.00 163.00   1.00    4.14    --   96.52  61.00   0.00   85
 18  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00   9.26   96
 19  \w     30.00 115.00   1.00    4.14    --   96.52 -61.00-150.00   85
 20  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00  56.23   96
 21  \w     29.00 125.00   1.00    4.14    --   96.52 -80.00-179.89   96
 22  \w    -53.00  31.00   1.00    1.04    --  -36.45  57.00 -90.00   84
 23  \w     10.00 104.00   1.00    1.04    --   36.45  77.00  90.00   94
 24  \w     20.00 104.00   1.00    1.04    --   36.45  57.00 150.00   84
 25  \w     20.00 104.00   1.00    1.04    --   36.45  57.00   0.00   84
 26  \w     10.00 104.00   1.00    1.04    --   36.45  77.00  30.00   94
 27  \w     10.00 104.00   1.00    1.04    --   36.45  77.00-180.00   94
 28  \w     79.00 165.00   1.00    4.14    --   96.52  45.00 -60.00   86
 29  \w     70.00 110.00   1.00    4.14    --   96.52  77.00 150.00   40
 30  \w     75.00 166.00   1.00    4.14    --   96.52  30.00 120.00   91
;
_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      0.0013121000
_diffrn_orient_matrix_UB_12      -0.0799932000
_diffrn_orient_matrix_UB_13      -0.0004306000
_diffrn_orient_matrix_UB_21      -0.0555097000
_diffrn_orient_matrix_UB_22      -0.0278928000
_diffrn_orient_matrix_UB_23      -0.0595429000
_diffrn_orient_matrix_UB_31      0.0923247000
_diffrn_orient_matrix_UB_32      -0.0003139000
_diffrn_orient_matrix_UB_33      -0.0316267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            84264
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        66.355
_diffrn_reflns_theta_max         66.355
_diffrn_reflns_theta_min         2.430
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.593
_exptl_absorpt_correction_T_max  0.925
_exptl_absorpt_correction_T_min  0.597
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.648
_exptl_crystal_description       block
_exptl_crystal_F_000             3096
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.037
_refine_diff_density_max         2.634
_refine_diff_density_min         -0.916
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1735
_refine_ls_number_reflns         21638
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0296
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0294P)^2^+12.5943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0692
_refine_ls_wR_factor_ref         0.0713
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19738
_reflns_number_total             21638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           1b
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        6301.76(13)
_cod_database_code               4517689
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C66H50BF24IrP2
_reflns_odcompleteness_completeness 99.11
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     62.30
_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
F16 \\sim F16A \\sim F17 \\sim F17A \\sim F18 \\sim F18A \\sim C58: within 2A
with sigma of 0.008 and sigma for terminal atoms of 0.016
Uanis(F19B) = Uanis(F20C)
Uanis(F19C) = Uanis(F21B)
Uanis(F21C) = Uanis(F20B)
3. Others
 Sof(F19C)=Sof(F20C)=Sof(F21C)=1-FVAR(1)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=FVAR(1)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C1B(H1B), C2B(H2B), C5B(H5B), C6B(H6B)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C3B(H3BA,H3BB), C4B(H4BA,
 H4BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C11B(H11B), C12B(H12B),
 C13B(H13B), C14B(H14B), C15B(H15B), C17B(H17B), C18B(H18B), C19B(H19B),
 C20B(H20B), C21B(H21B), C24B(H24B), C25B(H25B), C26B(H26B), C27B(H27B),
 C28B(H28B), C30B(H30B), C31B(H31B), C32B(H32B), C33B(H33B), C34B(H34B),
 C36(H36), C38(H38), C40(H40), C44(H44), C46(H46), C48(H48), C52(H52), C54(H54),
  C56(H56), C60(H60), C62(H62), C64(H64), C36B(H36B), C38B(H38B), C40B(H40B),
 C44B(H44B), C46B(H46B), C48B(H48B), C52B(H52B), C54B(H54B), C56B(H56B),
 C60B(H60B), C62B(H62B), C64B(H64B)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C22(H22A,H22B,H22C), C9B(H9BA,H9BB,H9BC), C22B(H22D,H22E,H22F)
;
_shelx_res_checksum              98504
_shelx_hkl_checksum              84624
_olex2_date_sample_data_collection 2018-09-20
_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 1.195
_oxdiff_exptl_absorpt_empirical_full_min 0.908