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_4517693
_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 H30 F36 Ir P2, C H2 Cl2, C32 H12 B F24'
_chemical_formula_sum            'C89 H44 B Cl2 F60 Ir P2'
_chemical_formula_weight         2589.09
_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             2017-08-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.6412(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.33896(13)
_cell_length_b                   13.16861(12)
_cell_length_c                   38.4041(3)
_cell_measurement_reflns_used    51152
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      30.1510
_cell_measurement_theta_min      3.1430
_cell_volume                     9270.73(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 16.3012
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.899
_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      1.00  85.00   0.30    7.00    --   18.18  57.00 120.00  280
  2  \w      1.00  85.00   0.30    7.00    --   18.18  57.00-150.00  280
  3  \w    -88.00  50.00   0.30    7.00    --  -18.49   0.00-150.00  460
  4  \w    -35.00  49.00   0.30    7.00    --  -18.49  57.00-150.00  280
  5  \w     -9.00  68.10   0.30    7.00    --   18.18  77.00   0.00  257
  6  \w    -49.00  44.00   0.30    7.00    --   18.18 -77.00   0.00  310
  7  \w     34.00  91.00   0.30    7.00    --   18.18-178.00   0.00  190
  8  \w    -86.00 -60.80   0.30    7.00    --  -18.33 -57.00-150.00   84
  9  \w    -67.00 -18.10   0.30    7.00    --  -18.33 117.00  71.00  163
;
_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      -0.0173161000
_diffrn_orient_matrix_UB_12      -0.0061324000
_diffrn_orient_matrix_UB_13      0.0161453000
_diffrn_orient_matrix_UB_21      0.0291985000
_diffrn_orient_matrix_UB_22      0.0261056000
_diffrn_orient_matrix_UB_23      0.0085828000
_diffrn_orient_matrix_UB_31      -0.0185535000
_diffrn_orient_matrix_UB_32      0.0467211000
_diffrn_orient_matrix_UB_33      -0.0026635000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.899
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            142463
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.419
_diffrn_reflns_theta_min         2.875
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.701
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.540
_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    1.855
_exptl_crystal_description       block
_exptl_crystal_F_000             5056
_exptl_crystal_recrystallization_method
'from a saturated dichloromethane solution'
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.199
_refine_diff_density_min         -1.525
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1542
_refine_ls_number_reflns         25251
_refine_ls_number_restraints     544
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0409
_refine_ls_shift/su_max          0.005
_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^+24.6040P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22892
_reflns_number_total             25251
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           1f
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        9270.74(12)
_cod_database_code               4517693
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C89H44BCl2F60IrP2
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.633
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F34B-C56B \\sim F34-C56 \\sim F35B-C56B \\sim F35-C56 \\sim F36B-C56B \\sim
F36-C56
 with sigma of 0.02
 F33B-C55B \\sim F31B-C55B \\sim F32B-C55B \\sim F32-C55 \\sim F33-C55 \\sim
F31-C55
 with sigma of 0.02
 C55-C51 \\sim C55B-C51
 with sigma of 0.02
 C54B-C53B \\sim C52B-C53B \\sim C52B-C51B \\sim C50B-C51B \\sim C51-C50 \\sim
C52-C51 \\sim C52-C53 ~
 C53-C54 \\sim C49-C54B \\sim C49-C54 \\sim C49-C50 \\sim C49-C50B
 with sigma of 0.02
 C55-C51 \\sim C51B-C55B \\sim C53B-C56B \\sim C56-C53
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F31 \\sim F31B \\sim F32 \\sim F32B \\sim F33 \\sim F33B \\sim F34 \\sim F34B
\\sim F35 \\sim F35B \\sim F36 \\sim F36B \\sim C49 \\sim C50 \\sim C50B \\sim
C51 \\sim C51B \\sim C52 \\sim C52B \\sim C53 \\sim C53B \\sim C54 \\sim C54B
\\sim C55 \\sim C55B \\sim C56 \\sim C56B: within 1.7A with sigma of 0.008 and
sigma for terminal atoms of 0.016
F16 \\sim F16B \\sim F17 \\sim F17B \\sim F18 \\sim F18B \\sim C32: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Others
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(1)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=Sof(F36)=Sof(C50)=Sof(H50)=
 Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(C56)=1-
 FVAR(2)
 Sof(F31B)=Sof(F32B)=Sof(F33B)=Sof(F34B)=Sof(F35B)=Sof(F36B)=Sof(C50B)=
 Sof(H50B)=Sof(C51B)=Sof(C52B)=Sof(H52B)=Sof(C53B)=Sof(C54B)=Sof(H54B)=
 Sof(C55B)=Sof(C56B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C89(H89A,H89B)
5.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), C50B(H50B), C52(H52), C52B(H52B), C54(H54), C54B(H54B), C58(H58),
 C60(H60), C62(H62), C66(H66), C68(H68), C70(H70), C74(H74), C76(H76), C78(H78),
  C82(H82), C84(H84), C86(H86)
;
_shelx_res_checksum              50609
_shelx_hkl_checksum              13869
_olex2_date_sample_data_collection 2017-08-15
_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 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.715