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_7119566
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-12-10 deposited with the CCDC.
2017-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90.9277(10)
_cell_angle_beta                 110.5820(12)
_cell_angle_gamma                103.1837(11)
_cell_formula_units_Z            2
_cell_length_a                   14.26025(19)
_cell_length_b                   15.46771(19)
_cell_length_c                   17.3328(2)
_cell_measurement_reflns_used    39091
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.9000
_cell_measurement_theta_min      3.7850
_cell_volume                     3465.26(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43g (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43g (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43g (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
_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 0.981
_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    -64.00  30.00   1.00    1.30    --  -37.09  77.00 120.00   94
  2  \w    -54.00  30.00   1.00    1.30    --  -37.09  57.00   0.00   84
  3  \w    -54.00  30.00   1.00    1.30    --  -37.09  57.00 -30.00   84
  4  \w   -104.00 -20.00   1.00    1.30    --  -37.09 -57.00-180.00   84
  5  \w   -104.00 -20.00   1.00    1.30    --  -37.09 -57.00  30.00   84
  6  \w     41.00 132.00   1.00    5.19    --  111.00 -30.00  30.00   91
  7  \w     42.00 144.00   1.00    5.19    --  111.00 -89.00 151.26  102
  8  \w     84.00 178.00   1.00    5.19    --  111.00  77.00  60.00   94
  9  \w    -64.00  30.00   1.00    1.30    --  -37.09  77.00  30.00   94
 10  \w      4.00  33.00   1.00    1.30    --   37.09  88.00  43.50   29
 11  \w    -30.00  54.00   1.00    1.30    --   37.09 -57.00 120.00   84
 12  \w     18.00 106.00   1.00    1.30    --   37.09  38.00 120.00   88
 13  \w     20.00 104.00   1.00    1.30    --   37.09  57.00 -60.00   84
 14  \w     20.00 104.00   1.00    1.30    --   37.09  57.00  30.00   84
 15  \w    -30.00  54.00   1.00    1.30    --   37.09 -57.00 150.00   84
 16  \w      4.00  33.00   1.00    1.30    --   37.09  88.00-158.52   29
 17  \w      3.00  32.00   1.00    1.30    --   37.09  90.00 -80.58   29
 18  \w    -30.00  54.00   1.00    1.30    --   37.09 -57.00-150.00   84
 19  \w    -34.00  66.00   1.00    1.30    --   37.09 -19.00-180.00  100
 20  \w    -30.00  64.00   1.00    1.30    --   37.09 -77.00  30.00   94
 21  \w    -12.00  71.00   1.00    1.30    --   37.09 -90.00-148.33   83
 22  \w    -30.00  54.00   1.00    1.30    --   37.09 -57.00  90.00   84
 23  \w     42.00 145.00   1.00    5.19    --  111.00 -90.00  51.44  103
 24  \w     42.00 145.00   1.00    5.19    --  111.00 -90.00 141.72  103
 25  \w     41.00 132.00   1.00    5.19    --  111.00 -30.00 120.00   91
 26  \w     43.00 138.00   1.00    5.19    --  111.00 -77.00-180.00   95
 27  \w     43.00 128.00   1.00    5.19    --  111.00 -45.00 -90.00   85
 28  \w     94.00 178.00   1.00    5.19    --  111.00  45.00  60.00   84
 29  \w     42.00 144.00   1.00    5.19    --  111.00 -89.00 124.82  102
 30  \w     94.00 178.00   1.00    5.19    --  111.00  45.00-180.00   84
 31  \w     73.00 178.00   1.00    5.19    --  111.00  15.00   0.00  105
 32  \w     84.00 178.00   1.00    5.19    --  111.00  77.00   0.00   94
 33  \w     90.00 178.00   1.00    5.19    --  111.00  30.00 -60.00   88
 34  \w     42.00 145.00   1.00    5.19    --  111.00 -90.00 -34.19  103
 35  \w     42.00 145.00   1.00    5.19    --  111.00 -90.00-107.45  103
 36  \w    -64.00  30.00   1.00    1.30    --  -37.09  77.00   0.00   94
 37  \w   -108.00  -8.00   1.00    1.30    --  -37.09 -19.00-180.00  100
 38  \w   -105.00 -10.00   1.00    1.30    --  -37.09 -77.00 -90.00   95
 39  \w   -105.00 -10.00   1.00    1.30    --  -37.09 -77.00 150.00   95
 40  \w   -105.00 -10.00   1.00    1.30    --  -37.09 -77.00 120.00   95
 41  \w   -104.00 -20.00   1.00    1.30    --  -37.09 -57.00-150.00   84
 42  \w   -105.00 -10.00   1.00    1.30    --  -37.09 -77.00   0.00   95
 43  \w   -105.00 -10.00   1.00    1.30    --  -37.09 -77.00  30.00   95
 44  \w   -104.00 -20.00   1.00    1.30    --  -37.09 -57.00 120.00   84
 45  \w    -12.00  71.00   1.00    1.30    --   37.09 -90.00  35.81   83
 46  \w     10.00 105.00   1.00    1.30    --   37.09  77.00-180.00   95
 47  \w     18.00 106.00   1.00    1.30    --   37.09  38.00  30.00   88
 48  \w     18.00 106.00   1.00    1.30    --   37.09  38.00 -60.00   88
 49  \w    -30.00  64.00   1.00    1.30    --   37.09 -77.00-120.00   94
 50  \w     10.00 105.00   1.00    1.30    --   37.09  77.00 120.00   95
 51  \w     10.00 105.00   1.00    1.30    --   37.09  77.00 150.00   95
;
_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      -0.0746887000
_diffrn_orient_matrix_UB_12      0.0152778000
_diffrn_orient_matrix_UB_13      -0.0847305000
_diffrn_orient_matrix_UB_21      0.0097529000
_diffrn_orient_matrix_UB_22      0.0953586000
_diffrn_orient_matrix_UB_23      0.0345796000
_diffrn_orient_matrix_UB_31      0.0923521000
_diffrn_orient_matrix_UB_32      0.0354375000
_diffrn_orient_matrix_UB_33      -0.0272181000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            65797
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.403
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.172
_exptl_absorpt_correction_T_max  0.856
_exptl_absorpt_correction_T_min  0.635
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43g (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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.632
_exptl_crystal_description       block
_exptl_crystal_F_000             1684
_exptl_crystal_recrystallization_method 'From diisopropylether'
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.055
_refine_diff_density_max         2.511
_refine_diff_density_min         -1.439
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         13690
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0393
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0437P)^2^+8.6568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0969
_refine_ls_wR_factor_ref         0.0997
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12682
_reflns_number_total             13690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc09838j2.cif
_cod_data_source_block           Complex_4
_cod_depositor_comments
'Adding full bibliography for 7119563--7119566.cif.'
_cod_original_cell_volume        3465.25(8)
_cod_database_code               7119566
_chemical_oxdiff_formula         C74H48B1F24Ir1N1O2P2
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 C74-F23 \\sim C74-F22 \\sim C74-F24
 with sigma of 0.02
 C74A-F23 \\sim C74A-F22A \\sim C74A-F24A
 with sigma of 0.02
 C74-C69 \\sim C74A-C69
 with sigma of 0.02
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C41-N1 \\sim N1-C41A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F22A \\sim F22: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C74A \\sim C74: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F24A \\sim F24: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C18 \\sim C18A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C42A \\sim C42: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C41A \\sim C41: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C20A \\sim C20: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C16A \\sim C16: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C17A \\sim C17: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C19A \\sim C19: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18)=Sof(H18)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(H20A)=Sof(F22A)=Sof(F24A)=Sof(C74A)=1-FVAR(1)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18A)=Sof(H18A)=Sof(C19)=Sof(H19)=
 Sof(C20)=Sof(H20)=Sof(F22)=Sof(F24)=Sof(C74)=FVAR(1)
 Sof(C41)=Sof(C42)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(2)
 Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C27(H27A,H27B), C28(H28A,H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 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), C16A(H16A), C17A(H17A),
 C18(H18), C19A(H19A), C20A(H20A), C16(H16), C17(H17), C18A(H18A), C19(H19),
 C20(H20), C44(H44), C46(H46), C48(H48), C52(H52), C54(H54), C56(H56), C60(H60),
  C62(H62), C64(H64), C68(H68), C70(H70), C72(H72)
5.c Idealised Me refined as rotating group:
 C42A(H42A,H42B,H42C), C42(H42D,H42E,H42F)
;
_shelx_res_checksum              74973
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-08-10
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.338
_oxdiff_exptl_absorpt_empirical_full_min 0.833