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_4517691
_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 H66 Ir P2, C32 H12 B F24'
_chemical_formula_sum            'C88 H78 B F24 Ir P2'
_chemical_formula_weight         1856.45
_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             2018-04-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                95.5387(14)
_cell_angle_beta                 104.5920(14)
_cell_angle_gamma                92.1533(14)
_cell_formula_units_Z            2
_cell_length_a                   12.9847(2)
_cell_length_b                   16.3076(3)
_cell_length_c                   19.9591(3)
_cell_measurement_reflns_used    39451
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.8720
_cell_measurement_theta_min      2.5970
_cell_volume                     4062.50(12)
_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 0.891
_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    -51.00  37.00   1.00    6.03    --   18.18 -38.00 -60.00   88
  2  \w    -20.00  57.00   1.00    6.03    --   18.18 -99.00 -90.00   77
  3  \w      1.00  85.00   1.00    6.03    --   18.18  57.00  90.00   84
  4  \w     34.00  91.00   1.00    6.03    --   18.18-178.00-120.00   57
  5  \w     -9.00  86.00   1.00    6.03    --   18.18  77.00-150.00   95
  6  \w     -9.00  86.00   1.00    6.03    --   18.18  77.00   0.00   95
  7  \w     -1.00  87.00   1.00    6.03    --   18.18  38.00 -30.00   88
  8  \w    -36.00  13.00   1.00    6.03    --  -18.49 -85.00  77.00   49
  9  \w    -20.00  57.00   1.00    6.03    --   18.18 -99.00  60.00   77
 10  \w    -20.00  40.00   1.00    6.03    --   18.18 -99.00-150.00   60
 11  \w     34.00  91.00   1.00    6.03    --   18.18-178.00 150.00   57
;
_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      -0.0335773000
_diffrn_orient_matrix_UB_12      -0.0309527000
_diffrn_orient_matrix_UB_13      -0.0237809000
_diffrn_orient_matrix_UB_21      -0.0342504000
_diffrn_orient_matrix_UB_22      -0.0013894000
_diffrn_orient_matrix_UB_23      0.0225576000
_diffrn_orient_matrix_UB_31      -0.0299819000
_diffrn_orient_matrix_UB_32      0.0309437000
_diffrn_orient_matrix_UB_33      -0.0170452000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.891
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            79719
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.263
_diffrn_reflns_theta_min         1.989
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.783
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89481
_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    1.518
_exptl_crystal_description       block
_exptl_crystal_F_000             1868
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.246
_exptl_crystal_size_min          0.205
_refine_diff_density_max         1.986
_refine_diff_density_min         -0.974
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1085
_refine_ls_number_reflns         21628
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0195P)^2^+4.5843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0606
_refine_ls_wR_factor_ref         0.0628
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19758
_reflns_number_total             21628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           1d
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        4062.49(12)
_cod_database_code               4517691
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C88H78BF24IrP2
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 F10, F10A, F11, F11A, F12, F12A, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C49(H49), C50(H50), C53(H53), C54(H54)
4.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C55(H55A,H55B), C56(H56A,H56B)
4.c 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), C26(H26), C28(H28), C30(H30), C34(H34), C36(H36), C38(H38), C42(H42),
  C44(H44), C46(H46), 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:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C)
;
_shelx_res_checksum              88937
_shelx_hkl_checksum              49777
_olex2_date_sample_data_collection 2018-04-07
_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 1.165
_oxdiff_exptl_absorpt_empirical_full_min 0.857