Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.
Iali, Wissam; Green, Gary G. R.; Hart, Sam J.; Whitwood, Adrian C.; Duckett, Simon B.; Inorganic chemistry 55 (2016) 11639–11643; doi:10.1021/acs.inorgchem.6b02560

data_4349350
_publ_section_title
;
 Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer
 Catalyst before Converting to a Binuclear C-H Bond Activation Product
 Responsible for Hydrogen Isotope Exchange.
;
_journal_issue                   22
_journal_name_full               'Inorganic chemistry'
_journal_page_first              11639
_journal_page_last               11643
_journal_paper_doi               10.1021/acs.inorgchem.6b02560
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C26 H38 Ir N2, F6 P, C6 H6'
_chemical_formula_sum            'C32 H44 F6 Ir N2 P'
_chemical_formula_weight         793.86
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.4575(4)
_cell_length_b                   17.2962(4)
_cell_length_c                   22.7986(5)
_cell_measurement_reflns_used    8392
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      70.5580
_cell_measurement_theta_min      6.2500
_cell_volume                     6489.7(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     30.00  73.00   1.00   60.00    --   54.00 -57.00   0.00   43
  2  \w     41.00  94.00   1.00   60.00    --  108.00 -25.00   0.00   53
  3  \w     43.00  72.00   1.00   60.00    --  108.00 -25.00  90.00   29
  4  \w     39.00 104.00   1.00   60.00    --  108.00 -50.00 150.00   65
  5  \w     72.00 115.00   1.00   60.00    --  108.00-111.00 150.00   43
  6  \w     52.00 115.00   1.00   60.00    --  108.00-111.00  30.00   63
  7  \w     38.00  67.00   1.00   60.00    --  108.00 -25.00 -60.00   29
  8  \w     37.00  85.00   1.00   60.00    --  108.00 -37.00 -90.00   48
  9  \w     53.00 104.00   1.00   60.00    --  108.00 -50.00-150.00   51
 10  \w    101.00 138.00   1.00   60.00    --  108.00 -91.00-150.00   37
 11  \w     88.00 173.00   1.00   60.00    --  108.00  63.00  30.00   85
 12  \w    152.00 177.00   1.00   60.00    --  108.00 111.00 -30.00   25
 13  \w    106.00 132.00   1.00   60.00    --  108.00 111.00-150.00   26
 14  \w    100.00 139.00   1.00   60.00    --  108.00 111.00 -30.00   39
 15  \w     47.00 102.00   1.00   60.00    --   54.00  57.00 120.00   55
 16  \w     25.00 123.00   1.00   60.00    --   54.00  77.00   0.00   98
 17  \w     -7.00  68.00   1.00   15.00    --    0.00  57.00-150.00   75
 18  \w    -26.00  40.00   1.00   15.00    --    0.00  77.00 -30.00   66
 19  \w     23.00 109.00   1.00   60.00    --   54.00-125.00-150.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0921802000
_diffrn_orient_matrix_UB_12      -0.0043515000
_diffrn_orient_matrix_UB_13      0.0111379000
_diffrn_orient_matrix_UB_21      0.0059504000
_diffrn_orient_matrix_UB_22      0.0885404000
_diffrn_orient_matrix_UB_23      -0.0054796000
_diffrn_orient_matrix_UB_31      -0.0148987000
_diffrn_orient_matrix_UB_32      0.0079069000
_diffrn_orient_matrix_UB_33      0.0665088000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25465
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.878
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.940
_exptl_absorpt_correction_T_max  0.912
_exptl_absorpt_correction_T_min  0.341
_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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.625
_exptl_crystal_description       needle
_exptl_crystal_F_000             3168
_exptl_crystal_recrystallization_method 'Solvent evaporation from benzene'
_exptl_crystal_size_max          0.193
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.008
_refine_diff_density_max         1.551
_refine_diff_density_min         -0.848
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         5800
_refine_ls_number_restraints     81
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0293
_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^)+(0.0455P)^2^+2.8239P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0783
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4503
_reflns_number_total             5800
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b02560_si_004.cif
_cod_data_source_block           complex_5
_cod_original_cell_volume        6489.6(3)
_cod_database_code               4349350
_chemical_oxdiff_formula         'C32 H44 F6 Ir1 N2 P1'
_chemical_oxdiff_usercomment     'Wissam Ir(coe)2(py)2 PF6'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C12B-C11 \\sim C12A-C11 \\sim C12B-C13B \\sim C12A-C13A \\sim C13B-C14B \\sim
C13A-C14A \\sim C15A-
 C14A \\sim C15A-C14B \\sim C16-C15A
 with sigma of 0.005
 C12B-C13B \\sim C12A-C13A \\sim C13B-C14B \\sim C13A-C14A \\sim C15B-C14B
\\sim C15A-C14A \\sim C16-
 C15B \\sim C16-C15A \\sim C12B-C11 \\sim C12A-C11
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C6A) = Uanis(C6B)
Uanis(C5A) = Uanis(C5B)
Uanis(C32B) = Uanis(C32A)
Uanis(C29A) = Uanis(C28B)
Uanis(C31A) = Uanis(C31B)
Uanis(C12A) = Uanis(C12B)
Uanis(C13A) = Uanis(C13B)
Uanis(C14A) = Uanis(C14B)
Uanis(C15A) = Uanis(C15B)
Uanis(F1A) = Uanis(F6A)
Uanis(F1B) = Uanis(F6B)
Uanis(F2A) = Uanis(F4A)
Uanis(F2B) = Uanis(F4B)
Uanis(F3A) = Uanis(F5A)
Uanis(F3B) = Uanis(F5B)
4. Others
 Sof(H4B)=Sof(HC)=Sof(C5B)=Sof(HE)=Sof(HF)=Sof(C6B)=Sof(HH)=Sof(HI)=Sof(H7B)=
 Sof(HJ)=1-FVAR(1)
 Sof(H4A)=Sof(HB)=Sof(C5A)=Sof(HD)=Sof(H5A)=Sof(C6A)=Sof(HG)=Sof(H6A)=
 Sof(H7AA)=Sof(H7AB)=FVAR(1)
 Sof(C29B)=Sof(H29B)=Sof(C28B)=Sof(H28B)=Sof(C27B)=Sof(H5CA)=Sof(C32B)=
 Sof(H6CA)=Sof(C31B)=Sof(H7CA)=Sof(C30B)=Sof(H8CA)=1-FVAR(2)
 Sof(C30A)=Sof(H30A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(H3CA)=Sof(C27A)=
 Sof(H4CA)=Sof(C32A)=Sof(H32A)=Sof(C31A)=Sof(H31A)=FVAR(2)
 Sof(HQ)=Sof(HR)=Sof(C12B)=Sof(HU)=Sof(HV)=Sof(C13B)=Sof(HY)=Sof(HZ)=Sof(C14B)=
 Sof(H2AA)=Sof(H3AA)=Sof(C15B)=Sof(H6AA)=Sof(H8AA)=Sof(H1BA)=Sof(H2BA)=1-FVAR(3)
 Sof(HO)=Sof(HP)=Sof(C12A)=Sof(HS)=Sof(HT)=Sof(C13A)=Sof(HW)=Sof(HX)=Sof(C14A)=
 Sof(H0AA)=Sof(H1AA)=Sof(C15A)=Sof(H4AA)=Sof(H5AA)=Sof(H9AA)=Sof(H0BA)=FVAR(3)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(4)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C1(H), C2(HA), C9(HM), C10(HN)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,HB), C4(H4B,HC), C5A(HD,H5A), C5B(HE,HF), C6A(HG,H6A),
 C6B(HH,HI), C7(H7AA,H7AB), C7(H7B,HJ), C8(HK,HL), C11(HO,HP), C11(HQ,HR),
 C12A(HS,HT), C12B(HU,HV), C13A(HW,HX), C13B(HY,HZ), C14A(H0AA,H1AA), C14B(H2AA,
 H3AA), C15A(H4AA,H5AA), C15B(H6AA,H8AA), C16(H9AA,H0BA), C16(H1BA,H2BA)
5.c Aromatic/amide H refined with riding coordinates:
 C17(H3BA), C18(H4BA), C19(H5BA), C20(H6BA), C21(H7BA), C22(H8BA), C23(H9BA),
 C24(H0CA), C25(H1CA), C26(H2CA), C30A(H30A), C29A(H29A), C28A(H3CA),
 C27A(H4CA), C32A(H32A), C31A(H31A), C29B(H29B), C28B(H28B), C27B(H5CA),
 C32B(H6CA), C31B(H7CA), C30B(H8CA)
5.d Fitted hexagon refined as free rotating group:
 C30A(C29A,C28A,C27A,C32A,C31A), C29B(C28B,C27B,C32B,C31B,C30B)
;
_shelx_res_checksum              50630
_shelx_hkl_checksum              18645
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-06-02
_olex2_exptl_crystal_mounting_method '100 /mm micromount'
_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 1.357
_oxdiff_exptl_absorpt_empirical_full_min 0.819