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_4517690
_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         'C24 H34 Ir P2, C32 H12 B F24, 0.5(C4 H10 O)'
_chemical_formula_sum            'C58 H51 B F24 Ir O0.5 P2'
_chemical_formula_weight         1476.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.2564(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.17636(16)
_cell_length_b                   38.6268(5)
_cell_length_c                   12.77708(18)
_cell_measurement_reflns_used    41471
_cell_measurement_temperature    100.4(8)
_cell_measurement_theta_max      27.6550
_cell_measurement_theta_min      2.5470
_cell_volume                     5913.47(14)
_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      100.4(8)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.3012
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      2.00  86.00   1.00   12.00    --   18.25  57.00 150.00   84
  2  \w      2.00  86.00   1.00   12.00    --   18.25  57.00-120.00   84
  3  \w    -49.00  45.00   1.00   12.00    --   18.25 -77.00  30.00   94
  4  \w    -49.00  35.00   1.00   12.00    --   18.25 -57.00 -30.00   84
  5  \w    -48.00  27.00   1.00   12.00    --  -18.49  19.00 -30.00   75
  6  \w      3.00  68.00   1.00   12.00    --   18.25  57.00 -30.00   65
  7  \w     18.00  44.00   1.00   12.00    --   18.25 -99.00-180.00   26
  8  \w     58.00  83.00   1.00   12.00    --   18.25  38.00  60.00   25
  9  \w     54.00  80.00   1.00   12.00    --   18.25 178.00 -30.00   26
 10  \w     -9.00  17.00   1.00   12.00    --   18.25  19.00 120.00   26
 11  \w     -4.00  65.00   1.00   12.00    --   18.25  77.00  30.00   69
;
_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      -0.0383809000
_diffrn_orient_matrix_UB_12      0.0136917000
_diffrn_orient_matrix_UB_13      -0.0150336000
_diffrn_orient_matrix_UB_21      -0.0448641000
_diffrn_orient_matrix_UB_22      -0.0112278000
_diffrn_orient_matrix_UB_23      0.0050247000
_diffrn_orient_matrix_UB_31      0.0045105000
_diffrn_orient_matrix_UB_32      0.0048390000
_diffrn_orient_matrix_UB_33      0.0541523000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -50
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            85932
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.129
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.427
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.659
_exptl_crystal_description       block
_exptl_crystal_F_000             2924
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.297
_exptl_crystal_size_min          0.255
_refine_diff_density_max         0.763
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.452(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1625
_refine_ls_number_reflns         27088
_refine_ls_number_restraints     175
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0391
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0287P)^2^+1.1393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0689
_refine_ls_wR_factor_ref         0.0700
_reflns_Friedel_coverage         0.971
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                25700
_reflns_number_total             27088
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           1c
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        5913.46(15)
_cod_original_formula_sum        'C58 H51 B F24 Ir O0.50 P2'
_cod_database_code               4517690
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C58H80BF24IrO1P2
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.459
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.548(4)
 0.452(4)
2. 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
3. Uiso/Uaniso restraints and constraints
F4A \\sim F5A \\sim F6A \\sim C32A \\sim F4B \\sim F5B \\sim F6B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
F19A \\sim F20A \\sim F21A \\sim C55A \\sim F19B \\sim F20B \\sim F21B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C54) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 F7, F8, F9, C39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(1)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(2)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C1A(H1A), C2A(H2A), C5A(H5A), C6A(H6A)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C3A(H3AB,H3AA), C4A(H4AB,
 H4AA), C7A(H7AA,H7AB), C8A(H8AA,H8AB), C58(H58A,H58B), C59(H59A,H59B)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A),
 C16A(H16A), C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A),
 C26(H26), C28(H28), C30(H30), C34(H34), C36(H36), C38(H38), C42(H42), C44(H44),
  C46(H46), C50(H50), C52(H52), C54(H54), C26A(H26A), C28A(H28A), C30A(H30A),
 C34A(H34A), C36A(H36A), C38A(H38A), C42A(H42A), C44A(H44A), C46A(H46A),
 C50A(H50A), C52A(H52A), C54A(H54A)
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10D,H10E,H10F), C17(H17D,H17E,H17F), C18(H18D,H18E,
 H18F), C9A(H9AA,H9AB,H9AC), C10A(H10A,H10B,H10C), C17A(H17A,H17B,H17C),
 C18A(H18A,H18B,H18C), C57(H57A,H57B,H57C), C60(H60A,H60B,H60C)
;
_shelx_res_checksum              94840
_shelx_hkl_checksum              32902
_olex2_date_sample_data_collection 2018-12-12
_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 1.630
_oxdiff_exptl_absorpt_empirical_full_min 0.589