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_4517701
_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         'C54 H37 F36 Ir P2 Si'
_chemical_formula_sum            'C54 H37 F36 Ir P2 Si'
_chemical_formula_weight         1652.06
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.527(3)
_cell_angle_beta                 94.566(3)
_cell_angle_gamma                101.595(3)
_cell_formula_units_Z            2
_cell_length_a                   13.9408(4)
_cell_length_b                   14.1616(4)
_cell_length_c                   16.2996(5)
_cell_measurement_reflns_used    23383
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.3750
_cell_measurement_theta_min      2.8160
_cell_volume                     3051.57(17)
_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 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   10.00    --   18.25  57.00 -90.00   84
  2  \w    -20.00  57.00   1.00   10.00    --   18.25 -99.00-150.00   77
  3  \w     -8.00  86.00   1.00   10.00    --   18.25  77.00   0.00   94
  4  \w      2.00  86.00   1.00   10.00    --   18.25  57.00 -60.00   84
  5  \w     -8.00  86.00   1.00   10.00    --   18.25  77.00 120.00   94
  6  \w     35.00  90.00   1.00   10.00    --   18.25 178.00-180.00   55
  7  \w    -88.00  51.00   1.00   10.00    --  -18.49   0.00 -90.00  139
  8  \w     -1.00  87.00   1.00   10.00    --   18.25  38.00-150.00   88
  9  \w     35.00  82.00   1.00   10.00    --   18.25 178.00  30.00   47
 10  \w    -20.00  57.00   1.00   10.00    --   18.25 -99.00   0.00   77
 11  \w    -20.00  57.00   1.00   10.00    --   18.25 -99.00 -90.00   77
 12  \w    -20.00  57.00   1.00   10.00    --   18.25 -99.00 120.00   77
 13  \w     35.00  90.00   1.00   10.00    --   18.25 178.00 150.00   55
 14  \w    -20.00  57.00   1.00   10.00    --   18.25 -99.00  60.00   77
;
_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      0.0423121000
_diffrn_orient_matrix_UB_12      -0.0167351000
_diffrn_orient_matrix_UB_13      0.0124236000
_diffrn_orient_matrix_UB_21      -0.0188100000
_diffrn_orient_matrix_UB_22      -0.0463247000
_diffrn_orient_matrix_UB_23      -0.0293865000
_diffrn_orient_matrix_UB_31      0.0244768000
_diffrn_orient_matrix_UB_32      0.0185980000
_diffrn_orient_matrix_UB_33      -0.0316670000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0757
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            62109
_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         26.372
_diffrn_reflns_theta_min         2.371
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.407
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.599
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.798
_exptl_crystal_description       block
_exptl_crystal_F_000             1612
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.214
_exptl_crystal_size_min          0.184
_refine_diff_density_max         2.328
_refine_diff_density_min         -1.389
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1054
_refine_ls_number_reflns         12490
_refine_ls_number_restraints     646
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0454P)^2^+1.8914P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0868
_refine_ls_wR_factor_ref         0.0912
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11104
_reflns_number_total             12490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01718_si_002.cif
_cod_data_source_block           21a
_cod_depositor_comments
'Adding full bibliography for 4517689--4517702.cif.'
_cod_original_cell_volume        3051.55(16)
_cod_database_code               4517701
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C54H33F36IrP2Si
_reflns_odcompleteness_completeness 99.93
_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, All Ir(H,H,H,H) groups
2. Restrained distances
 Ir1-HB \\sim Ir1-HC \\sim Ir1-HA \\sim Ir1-H
 with sigma of 0.02
 C30B-C27 \\sim C30-C27
 with sigma of 0.02
 F18-C30 \\sim F18B-C30B \\sim F16-C30 \\sim F16B-C30B \\sim F17-C30 \\sim
F17B-C30B
 with sigma of 0.02
3. Rigid bond restraints
 F31, F31B, F32, F32B, F33, F33B, F34, F34B, F35, F35B, F36, F36B, C47, C47B,
 C48, C48B, C49, C49B, C50, C50B, C51, C51B, C52, C52B, C53, C53B, C54, C54B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F7 \\sim F7B \\sim F8 \\sim F8B \\sim F9 \\sim F9B \\sim C21: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
F16 \\sim F16B \\sim F17 \\sim F17B \\sim F18 \\sim F18B \\sim C30 \\sim C30B:
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 \\sim F34 \\sim F34B
\\sim F35 \\sim F35B \\sim F36 \\sim F36B \\sim C47 \\sim C47B \\sim C48 \\sim
C48B \\sim C49 \\sim C49B \\sim C50 \\sim C50B \\sim C51 \\sim C51B \\sim C52
\\sim C52B \\sim C53 \\sim C53B \\sim C54 \\sim C54B: within 1.6A with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(1)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=Sof(C30B)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=Sof(C30)=FVAR(2)
 Sof(F31B)=Sof(F32B)=Sof(F33B)=Sof(F34B)=Sof(F35B)=Sof(F36B)=Sof(C47B)=
 Sof(C48B)=Sof(H48B)=Sof(C49B)=Sof(C50B)=Sof(H50B)=Sof(C51B)=Sof(C52B)=
 Sof(H52B)=Sof(C53B)=Sof(C54B)=1-FVAR(3)
 Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=Sof(F36)=Sof(C47)=Sof(C48)=
 Sof(H48)=Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(C54)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C12(H12), C16(H16), C18(H18), C20(H20), C24(H24), C26(H26),
 C28(H28), C32(H32), C34(H34), C36(H36), C40(H40), C42(H42), C44(H44), C48(H48),
  C48B(H48B), C50(H50), C50B(H50B), C52(H52), C52B(H52B)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              61909
_shelx_hkl_checksum              92918
_olex2_date_sample_data_collection 2019-06-28
_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 2.036
_oxdiff_exptl_absorpt_empirical_full_min 0.415