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_7119564
_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         'C40 H32 Ir O2 P2, C32 H12 B F24, C2 H5 O0.5'
_chemical_formula_sum            'C74 H49 B F24 Ir O2.5 P2'
_chemical_formula_weight         1699.08
_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             2016-05-24
_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                88.6800(14)
_cell_angle_beta                 89.2622(14)
_cell_angle_gamma                78.5165(14)
_cell_formula_units_Z            2
_cell_length_a                   13.2902(2)
_cell_length_b                   16.0229(3)
_cell_length_c                   16.6282(3)
_cell_measurement_reflns_used    39061
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.9500
_cell_measurement_theta_min      3.5150
_cell_volume                     3469.01(11)
_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 0.895
_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     -8.00  84.00   1.00   22.50    --   17.49  77.00 150.00   92
  2  \w     -8.00  86.00   1.00   22.50    --   17.49  19.00   0.00   94
  3  \w      3.00  83.00   1.00   22.50    --   17.49  57.00-120.00   80
  4  \w     -8.00  84.00   1.00   22.50    --   17.49  77.00   0.00   92
  5  \w      3.00  83.00   1.00   22.50    --   17.49  57.00  90.00   80
  6  \w      3.00  83.00   1.00   22.50    --   17.49  57.00 -30.00   80
  7  \w    -33.00  48.00   1.00   22.50    --  -17.80  57.00 -30.00   81
  8  \w    -48.00  32.00   1.00   22.50    --   17.49 -57.00-150.00   80
  9  \w    -49.00  43.00   1.00   22.50    --   17.49 -77.00 150.00   92
 10  \w    -49.00  43.00   1.00   22.50    --   17.49 -77.00 -60.00   92
 11  \w    -47.00  36.00   1.00   22.50    --   17.49 -64.00  66.00   83
 12  \w    -43.00  41.00   1.00   22.50    --  -17.80  77.00   0.00   84
;
_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      0.0372462000
_diffrn_orient_matrix_UB_12      -0.0291034000
_diffrn_orient_matrix_UB_13      0.0221574000
_diffrn_orient_matrix_UB_21      0.0396897000
_diffrn_orient_matrix_UB_22      0.0134657000
_diffrn_orient_matrix_UB_23      -0.0226506000
_diffrn_orient_matrix_UB_31      0.0018916000
_diffrn_orient_matrix_UB_32      0.0318288000
_diffrn_orient_matrix_UB_33      0.0285774000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            83918
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.303
_diffrn_reflns_theta_min         2.984
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.083
_exptl_absorpt_correction_T_max  0.958
_exptl_absorpt_correction_T_min  0.807
_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    1.627
_exptl_crystal_description       needle
_exptl_crystal_F_000             1682
_exptl_crystal_size_max          0.239
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.793
_refine_diff_density_min         -1.177
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     961
_refine_ls_number_reflns         18625
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0250P)^2^+6.0940P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0695
_refine_ls_wR_factor_ref         0.0719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16856
_reflns_number_total             18625
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc09838j2.cif
_cod_data_source_block           Complex_2
_cod_depositor_comments
'Adding full bibliography for 7119563--7119566.cif.'
_cod_original_cell_volume        3469.02(10)
_cod_original_formula_sum        'C74 H49 B F24 Ir O2.50 P2'
_cod_database_code               7119564
_chemical_oxdiff_formula         C40H32IrO2P2,C32H12BF24,C2H5O0.5
_reflns_odcompleteness_completeness 99.86
_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,H,H,H) groups
2. Others
 Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(C73A)=Sof(H73C)=Sof(H73D)=1-FVAR(1)
 Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C73)=Sof(H73A)=Sof(H73B)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C22(H22A,H22B), C73(H73A,H73B), C73A(H73C,H73D)
3.b Me refined with riding coordinates:
 C74(H74A,H74B,H74C), C74(H74D,H74E,H74F)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C24(H24), C25(H25), C26(H26),
  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)
;
_shelx_res_checksum              1539
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-05
_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 1.527
_oxdiff_exptl_absorpt_empirical_full_min 0.615