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_7049781
_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         'C30 H23 Br Ir N5, C H Cl3'
_chemical_formula_sum            'C31 H24 Br Cl3 Ir N5'
_chemical_formula_weight         845.01
_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   mixed
_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                 105.7660(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.0167(3)
_cell_length_b                   12.4881(2)
_cell_length_c                   19.1229(3)
_cell_measurement_reflns_used    12399
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.8660
_cell_measurement_theta_min      4.2520
_cell_volume                     3221.38(10)
_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 0.992
_diffrn_measurement_details
;
  1 omega  -67.00  -18.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   57.0000  -60.0000 49

  2 omega  -50.00   -3.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   38.0000   90.0000 47

  3 omega  -48.00   34.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   38.0000 -150.0000 82

  4 omega    5.00   52.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -       40.3787  -99.0000  120.0000 47

  5 omega   77.00  121.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -       40.3787 -178.0000   60.0000 44

  6 omega   88.00  115.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000 -180.0000 27

  7 omega  105.00  156.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000  150.0000 51

  8 omega   63.00   89.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000   90.0000 26

  9 omega   81.00  107.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  -30.0000 26

 10 omega   60.00  107.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000   30.0000 47

 11 omega   42.00   82.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  120.0000 40

 12 omega   63.00   91.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   30.0000 28

 13 omega   36.00   63.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  -30.0000 27

 14 omega   82.00  177.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -180.0000 95

 15 omega   29.00   60.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  -60.0000 31

 16 omega   60.00   94.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000 -120.0000 34

 17 omega   36.00  101.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  120.0000 65

 18 omega   74.00  101.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  -60.0000 27

 19 omega   41.00   88.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   90.0000 47

 20 omega   30.00   64.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000 -120.0000 34

 21 omega   70.00  102.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000 -120.0000 32

 22 omega  101.00  127.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000   30.0000 26

 23 omega  149.00  175.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000   30.0000 26

 24 omega   61.00   96.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -120.0000 35

 25 omega   39.00   94.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   30.0000 55

 26 omega   47.00   73.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -22.0000   86.0000 26

 27 omega  -28.00   27.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   77.0000 -120.0000 55

 28 omega -105.00  -32.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787  -38.0000   60.0000 73

 29 omega  -41.00   18.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   38.0000    0.0000 59

 30 omega  -73.00  -40.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.3787   77.0000 -120.0000 33

 31 omega  103.00  129.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -       40.3787  178.0000 -180.0000 26

 32 omega   72.00   99.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -       40.3787 -178.0000  150.0000 27

 33 omega  145.00  176.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000    0.0000 31

 34 omega   88.00  114.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  120.0000 26

 35 omega  105.00  172.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000  120.0000 67

 36 omega   89.00  115.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  -90.0000 26

 37 omega   36.00   70.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  -90.0000 34

 38 omega  114.00  140.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000   30.0000 26

 39 omega   61.00   87.00   1.0000   25.5000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000   60.0000 26
;
_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      -0.0948776000
_diffrn_orient_matrix_UB_12      -0.0681569000
_diffrn_orient_matrix_UB_13      -0.0240050000
_diffrn_orient_matrix_UB_21      -0.0630227000
_diffrn_orient_matrix_UB_22      0.0994136000
_diffrn_orient_matrix_UB_23      0.0045237000
_diffrn_orient_matrix_UB_31      -0.0075075000
_diffrn_orient_matrix_UB_32      0.0260444000
_diffrn_orient_matrix_UB_33      -0.0801315000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0890
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            27500
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.329
_diffrn_reflns_theta_min         3.276
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.993
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27022
_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    1.742
_exptl_crystal_description       prism
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.399
_refine_diff_density_min         -3.067
_refine_diff_density_rms         0.178
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         6699
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0748P)^2^+16.4897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1331
_refine_ls_wR_factor_ref         0.1427
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5726
_reflns_number_total             6699
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01138b2.cif
_cod_data_source_block           ea-69
_cod_depositor_comments
'Adding full bibliography for 7049777--7049781.cif.'
_cod_database_code               7049781
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32 Br Ir Cl3 N5 O3'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 Br1A-C26A \\sim Br1A-C28A \\sim Br1-C28 \\sim Br1-C26
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(Br1A) = Uanis(Br1)
Uanis(C25) = Uanis(C25A)
Uanis(C24A) = Uanis(C24)
Uanis(C29A) = Uanis(C29)
Uanis(C27A) = Uanis(C27)
Uanis(C28A) = Uanis(C28)
Uanis(C26) = Uanis(C26A)
Uanis(N4) = Uanis(N4A)
4. Others
 Sof(Br1A)=Sof(N4A)=Sof(H4AA)=Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=
 Sof(H29A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=1-FVAR(1)
 Sof(N4)=Sof(H4)=Sof(C27)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C24)=
 Sof(C29)=Sof(H29)=Sof(C28)=Sof(H28)=Sof(Br1)=FVAR(1)
5.a Riding coordinates:
 N4A(H4AA)
5.b Ternary CH refined with riding coordinates:
 C1S(H1S)
5.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C14(H14), C16(H16), C15(H15), C13(H13), C8(H8), C19(H19), C21(H21),
 C20(H20), C2(H2), C10(H10), C11(H11), N4(H4), C5(H5), C3(H3), C4(H4A), C9(H9),
 C26(H26), C25(H25), C29(H29), C28(H28), C28A(H28A), C29A(H29A), C25A(H25A),
 C26A(H26A)
5.d Fitted hexagon refined as free rotating group:
 C27(C26,C25,C24,C29,C28), C27A(C28A,C29A,C24A,C25A,C26A)
5.e X=CH2 refined with riding coordinates:
 N3(H3A,H3B)
;
_shelx_res_checksum              31250
_shelx_fab_checksum              36966
_olex2_submission_special_instructions 'No special instructions were received'