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_7119563
_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 Cl Ir O2 P2, C6 H6'
_chemical_formula_sum            'C46 H38 Cl Ir O2 P2'
_chemical_formula_weight         912.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-09
_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
_cell_angle_beta                 97.6709(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.41924(8)
_cell_length_b                   18.7237(2)
_cell_length_c                   24.1937(2)
_cell_measurement_reflns_used    20842
_cell_measurement_temperature    100
_cell_measurement_theta_max      73.2500
_cell_measurement_theta_min      3.6790
_cell_volume                     3779.75(6)
_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      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 1.000
_diffrn_measured_fraction_theta_max 0.984
_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   -107.00 -17.00   1.00    3.64    --  -37.09 -34.00  31.00   90
  2  \w    -57.00  32.00   1.00    3.64    --  -37.09  34.00-171.00   89
  3  \w     17.00 107.00   1.00    3.64    --   37.09  34.00-171.00   90
  4  \w    -32.00  57.00   1.00    3.64    --   37.09 -34.00  31.00   89
  5  \w     41.00 131.00   1.00   14.58    --  111.00 -34.00  31.00   90
  6  \w     91.00 178.00   1.00   14.58    --  111.00  34.00-171.00   87
  7  \w     43.00 138.00   1.00   14.58    --  111.00 -77.00 -60.00   95
  8  \w   -108.00  -8.00   1.00    3.64    --  -37.09 -19.00-180.00  100
  9  \w    -64.00  30.00   1.00    3.64    --  -37.09  77.00 -60.00   94
 10  \w    -54.00  30.00   1.00    3.64    --  -37.09  57.00 -60.00   84
 11  \w     20.00 104.00   1.00    3.64    --   37.09  57.00  60.00   84
 12  \w     20.00 104.00   1.00    3.64    --   37.09  57.00-150.00   84
 13  \w     20.00 104.00   1.00    3.64    --   37.09  57.00 150.00   84
 14  \w     18.00 106.00   1.00    3.64    --   37.09  38.00  30.00   88
 15  \w     20.00 104.00   1.00    3.64    --   37.09  57.00 120.00   84
 16  \w     90.00 178.00   1.00   14.58    --  111.00  30.00 -60.00   88
 17  \w     43.00 138.00   1.00   14.58    --  111.00 -77.00-180.00   95
 18  \w     43.00 128.00   1.00   14.58    --  111.00 -45.00-180.00   85
 19  \w     43.00 138.00   1.00   14.58    --  111.00 -77.00  90.00   95
 20  \w     94.00 178.00   1.00   14.58    --  111.00  45.00   0.00   84
 21  \w     94.00 178.00   1.00   14.58    --  111.00  45.00-150.00   84
 22  \w    -64.00  30.00   1.00    3.64    --  -37.09  77.00  30.00   94
 23  \w    -64.00  30.00   1.00    3.64    --  -37.09  77.00-150.00   94
 24  \w    -64.00  30.00   1.00    3.64    --  -37.09  77.00 120.00   94
 25  \w     10.00  84.00   1.00    3.64    --   37.09  77.00   0.00   74
 26  \w     10.00 105.00   1.00    3.64    --   37.09  77.00 -90.00   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      -0.0966079000
_diffrn_orient_matrix_UB_12      -0.0122957000
_diffrn_orient_matrix_UB_13      -0.0579170000
_diffrn_orient_matrix_UB_21      0.1362122000
_diffrn_orient_matrix_UB_22      0.0340401000
_diffrn_orient_matrix_UB_23      -0.0276381000
_diffrn_orient_matrix_UB_31      0.0788475000
_diffrn_orient_matrix_UB_32      -0.0738828000
_diffrn_orient_matrix_UB_33      -0.0030697000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            36409
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.416
_diffrn_reflns_theta_min         3.687
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58334
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.603
_exptl_crystal_description       plate
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.089
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.594
_refine_diff_density_min         -1.395
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         7488
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0301
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0387P)^2^+4.6871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0748
_refine_ls_wR_factor_ref         0.0766
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6962
_reflns_number_total             7488
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc09838j2.cif
_cod_data_source_block           Complex_1
_cod_depositor_comments
'Adding full bibliography for 7119563--7119566.cif.'
_cod_original_cell_volume        3779.75(7)
_cod_database_code               7119563
_chemical_oxdiff_formula         C46H38Cl1Ir1O2P2
_reflns_odcompleteness_completeness 99.96
_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
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C23(H23A,H23B), C24(H24A,H24B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C26(H26), C27(H27), C28(H28),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C46(H46)
;
_shelx_res_checksum              5727
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-08-09
_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 1.948
_oxdiff_exptl_absorpt_empirical_full_min 0.533