Reversible alkoxycarbene formation by C-H activation of ethers via discrete, isolable intermediates.
Zhang, Yuanyuan; Schley, Nathan D.; Chemical communications (Cambridge, England) 53 (2017) 2130–2133; doi:10.1039/c6cc09838j

data_7119565
_publ_section_title
;
 Reversible alkoxycarbene formation by C-H activation of ethers via
 discrete, isolable intermediates.
;
_journal_issue                   13
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2130
_journal_page_last               2133
_journal_paper_doi               10.1039/c6cc09838j
_journal_volume                  53
_journal_year                    2017
_chemical_formula_moiety         'C42 H35 Ir N O2 P2, C32 H12 B F24'
_chemical_formula_sum            'C74 H47 B F24 Ir N O2 P2'
_chemical_formula_weight         1703.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2016-12-10 deposited with the CCDC.
2017-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                91.118(3)
_cell_angle_beta                 110.507(4)
_cell_angle_gamma                100.549(3)
_cell_formula_units_Z            2
_cell_length_a                   14.2753(5)
_cell_length_b                   15.5619(3)
_cell_length_c                   16.6725(7)
_cell_measurement_reflns_used    20914
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.7550
_cell_measurement_theta_min      3.5770
_cell_volume                     3396.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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      air
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.881
_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      0.00  81.00   1.00   25.00    --   15.35  57.00-150.00   81
  2  \w      0.00  81.00   1.00   25.00    --   15.35  57.00 150.00   81
  3  \w    -11.00  84.00   1.00   25.00    --   15.35  19.00   0.00   95
  4  \w    -10.00  82.00   1.00   25.00    --   15.35  77.00 -60.00   92
  5  \w      0.00  81.00   1.00   25.00    --   15.35  57.00  60.00   81
  6  \w    -81.00  -1.00   1.00   25.00    --  -15.58 -57.00-150.00   80
  7  \w    -30.00  50.00   1.00   25.00    --  -15.58  57.00 -30.00   80
  8  \w    -51.00  41.00   1.00   25.00    --   15.35 -77.00  90.00   92
  9  \w    -50.00 -13.00   1.00   25.00    --   15.35 -57.00 150.00   37
 10  \w    -49.00  34.00   1.00   25.00    --   15.35 -64.00-142.00   83
 11  \w    -20.00   7.00   1.00   25.00    --   15.35 -99.00   0.00   27
 12  \w    -20.00  52.00   1.00   25.00    --   15.35 -99.00-180.00   72
;
_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      -0.0262146000
_diffrn_orient_matrix_UB_12      -0.0444556000
_diffrn_orient_matrix_UB_13      -0.0094271000
_diffrn_orient_matrix_UB_21      0.0415639000
_diffrn_orient_matrix_UB_22      -0.0125363000
_diffrn_orient_matrix_UB_23      0.0323343000
_diffrn_orient_matrix_UB_31      -0.0228067000
_diffrn_orient_matrix_UB_32      0.0058253000
_diffrn_orient_matrix_UB_33      0.0307554000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            67020
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.445
_diffrn_reflns_theta_min         2.980
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.127
_exptl_absorpt_correction_T_max  0.904
_exptl_absorpt_correction_T_min  0.763
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       block
_exptl_crystal_F_000             1684
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.399
_refine_diff_density_min         -1.029
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1026
_refine_ls_number_reflns         16594
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0300P)^2^+6.3010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0858
_refine_ls_wR_factor_ref         0.0941
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13519
_reflns_number_total             16594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc09838j2.cif
_cod_data_source_block           Complex_3
_cod_depositor_comments
'Adding full bibliography for 7119563--7119566.cif.'
_cod_database_code               7119565
_chemical_oxdiff_formula         C74H46B1F24Ir1N1O2P2
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 Ir1-H
 1.47 with sigma of 0.02
3. Rigid bond restraints
 F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F12A \\sim F12: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
F10A \\sim F10: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
F11A \\sim F11: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C28 \\sim C28B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C8 \\sim C8B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F4 \\sim F5 \\sim F6 \\sim F4A \\sim F5A \\sim F6A: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C8B)=Sof(C28B)=Sof(H28B)=1-FVAR(1)
 Sof(C8)=Sof(H8)=Sof(C28)=FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(2)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(2)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(3)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C28B(H28B)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C27(H27A,H27B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37),
 C38(H38), C39(H39), C40(H40), C42(H42), C44(H44), C46(H46), C50(H50), C52(H52),
  C54(H54), C58(H58), C60(H60), C62(H62), C66(H66), C68(H68), C70(H70)
6.d Idealised Me refined as rotating group:
 C2A(H2AA,H2AB,H2AC)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-07-07
_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 1.610
_oxdiff_exptl_absorpt_empirical_full_min 0.463