Cleavage of acyclic diaminocarbene ligands at an iridium(iii) center. Recognition of a new reactivity mode for carbene ligands.
Kinzhalov, Mikhail A.; Eremina, Anzhelika A.; Smirnov, Andrey S.; Suslonov, Vitalii V.; Kukushkin, Vadim Yu; Luzyanin, Konstantin V.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 7571–7582; doi:10.1039/c9dt01138b

data_7049777
_publ_section_title
;
 Cleavage of acyclic diaminocarbene ligands at an iridium(iii) center.
 Recognition of a new reactivity mode for carbene ligands.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7571
_journal_page_last               7582
_journal_paper_doi               10.1039/c9dt01138b
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C36 H24 Br2 Ir N4, C F3 O3 S'
_chemical_formula_sum            'C37 H24 Br2 F3 Ir N4 O3 S'
_chemical_formula_weight         1013.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-06-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-06-01 deposited with the CCDC.    2019-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7060(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.89737(11)
_cell_length_b                   21.25955(19)
_cell_length_c                   15.54005(14)
_cell_measurement_reflns_used    24546
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.0110
_cell_measurement_theta_min      3.5320
_cell_volume                     3582.37(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
  1 omega  -48.00   30.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000 -120.0000 78

  2 omega   62.00   99.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354  178.0000   60.0000 37

  3 omega  122.00  148.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  150.0000 26

  4 omega   95.00  167.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000   30.0000 72

  5 omega  132.00  158.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -90.0000 26

  6 omega  142.00  168.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -120.0000 26

  7 omega  111.00  137.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000    0.0000 26

  8 omega  124.00  154.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000   60.0000 30

  9 omega  145.00  177.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  150.0000 32

 10 omega  126.00  177.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  120.0000 51

 11 omega   99.00  127.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -60.0000 28

 12 omega   93.00  119.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -90.0000 26

 13 omega   92.00  140.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -120.0000 48

 14 omega   83.00  108.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000    0.0000 -180.0000 25

 15 omega   49.00   96.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -60.0000 47

 16 omega   84.00  110.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000    0.0000 26

 17 omega   77.00  118.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000   60.0000 41

 18 omega   89.00  119.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  150.0000 30

 19 omega   57.00   85.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   90.0000 28

 20 omega   56.00   84.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000   60.0000 28

 21 omega  120.00  145.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000   60.0000 25

 22 omega   59.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000  150.0000 30

 23 omega   36.00   65.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   60.0000 29

 24 omega   39.00   65.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000   60.0000 26

 25 omega   37.00   87.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000    0.0000 50

 26 omega   44.00   80.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -90.0000 36

 27 omega   89.00  136.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000 -150.0000 47

 28 omega   69.00  121.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000 -120.0000 52

 29 omega   43.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -150.0000 46

 30 omega   43.00   71.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -90.0000 28

 31 omega   31.00   56.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000    0.0000 -180.0000 25

 32 omega   46.00   75.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000    0.0000 29

 33 omega -118.00  -16.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -19.0000   60.0000 102

 34 omega  -56.00   29.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   19.0000 -180.0000 85

 35 omega -114.00  -19.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -57.0000 -120.0000 95

 36 omega    4.00   39.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354  -99.0000   60.0000 35

 37 omega   83.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -60.0000 26

 38 omega   62.00   88.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -150.0000 26

 39 omega  129.00  155.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -60.0000 26

 40 omega  111.00  137.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000 -180.0000 26

 41 omega   81.00  107.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000   60.0000 26

 42 omega   83.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -90.0000 26

 43 omega  125.00  151.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -90.0000 26

 44 omega   72.00  121.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000   90.0000 49

 45 omega   83.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -120.0000 26

 46 omega   79.00  105.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 26

 47 omega   43.00   73.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   60.0000 30

 48 omega  136.00  174.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  120.0000 38

 49 omega   97.00  164.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000 -120.0000 67

 50 omega   87.00  139.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000   60.0000 52

 51 omega   87.00  113.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -60.0000 26

 52 omega   85.00  110.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -30.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1237663000
_diffrn_orient_matrix_UB_12      -0.0109559000
_diffrn_orient_matrix_UB_13      0.0377432000
_diffrn_orient_matrix_UB_21      -0.0629503000
_diffrn_orient_matrix_UB_22      0.0473549000
_diffrn_orient_matrix_UB_23      -0.0652391000
_diffrn_orient_matrix_UB_31      -0.0302349000
_diffrn_orient_matrix_UB_32      -0.0537439000
_diffrn_orient_matrix_UB_33      -0.0651168000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            44094
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.445
_diffrn_reflns_theta_min         3.534
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.877
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19435
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.879
_exptl_crystal_description       plate
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.771
_refine_diff_density_min         -1.047
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         7487
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0300
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0484P)^2^+5.9346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0793
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7117
_reflns_number_total             7487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01138b2.cif
_cod_data_source_block           ea-57
_cod_depositor_comments
'Adding full bibliography for 7049777--7049781.cif.'
_cod_database_code               7049777
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Ir Br2 N4 C36 S'
_reflns_odcompleteness_completeness 94.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C22(H22), C35(H35), C19(H19), C11(H11), C20(H20), C14(H14),
 C28(H28), C16(H16), C8(H8), C33(H33), C2(H2), C29(H29), C26(H26), C21(H21),
 C15(H15), C36(H36), C9(H9), C5(H5), C25(H25), C3(H3), C4(H4), C10(H10),
 C32(H32)
;
_shelx_res_checksum              50526
_olex2_submission_special_instructions 'No special instructions were received'