Dehydrogenation of Cyclic Amines by a Coordinatively Unsaturated Cp*Ir(III) Phosphoramidate Complex
Drover, Marcus W.; Schafer, Laurel L.; Love, Jennifer; Dalton Trans.  (2017) –; doi:10.1039/C7DT01499F

data_7043192
_publ_section_title
;
 Dehydrogenation of Cyclic Amines by a Coordinatively Unsaturated
 Cp*Ir(III) Phosphoramidate Complex
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01499F
_journal_year                    2017
_chemical_formula_moiety         'C18 H31.02 Ir N2, C32 H12 B F24'
_chemical_formula_sum            'C50 H43.01 B F24 Ir N2'
_chemical_formula_weight         1330.89
_chemical_name_systematic        '[Cp*Ir(H)(imine)2][BArF4]'
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-27
_audit_creation_method
;
Olex2 1.2
(compiled Dec 12 2016 15:38:10 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-03-09 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                94.122(3)
_cell_angle_beta                 110.854(3)
_cell_angle_gamma                103.523(3)
_cell_formula_units_Z            2
_cell_length_a                   12.7119(15)
_cell_length_b                   12.8605(16)
_cell_length_c                   17.518(2)
_cell_measurement_reflns_used    9799
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      28.885
_cell_measurement_theta_min      2.203
_cell_volume                     2563.9(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker-Nonius APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device
'Bruker-Nonius APEXII CCD area detector and D8 diffractometer'
_diffrn_measurement_device_type  'Apex Duo II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            52810
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.219
_diffrn_reflns_theta_min         1.653
_exptl_absorpt_coefficient_mu    2.729
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.5530
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0752 before and 0.0409 after correction.
The Ratio of minimum to maximum transmission is 0.7415.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.724
_exptl_crystal_description       block
_exptl_crystal_F_000             1310
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.854
_refine_diff_density_min         -0.938
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     942
_refine_ls_number_reflns         13832
_refine_ls_number_restraints     966
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0501P)^2^+6.8712P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.1005
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12467
_reflns_number_total             13832
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01499f2.cif
_cod_data_source_block           mo_jl191_0m_a
_cod_original_cell_volume        2563.8(5)
_cod_database_code               7043192
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C31) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H2)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(C18)=Sof(H18)=FVAR(1)
 Sof(N1)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22)=1-FVAR(2)
 Sof(N3)=Sof(H3)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
 Sof(F3A)=Sof(F1A)=Sof(F2A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(4)
 Fixed Sof: C1(0.68) H1A(0.68) H1B(0.68) H1C(0.68) C2(0.68) C3(0.68) C4(0.68)
 C5(0.68) C6(0.68) H6A(0.68) H6B(0.68) H6C(0.68) C7(0.68) C8(0.68) H8A(0.68)
 H8B(0.68) H8C(0.68) C9(0.68) H9A(0.68) H9B(0.68) H9C(0.68) C10(0.68)
 H10A(0.68) H10B(0.68) H10C(0.68) C27(0.32) C28(0.32) C29(0.32) C30(0.32)
 C31(0.32) C32(0.32) H32A(0.32) H32B(0.32) H32C(0.32) C33(0.32) H33A(0.32)
 H33B(0.32) H33C(0.32) C34(0.32) H34A(0.32) H34B(0.32) H34C(0.32) C35(0.32)
 H35A(0.32) H35B(0.32) H35C(0.32) C36(0.32) H36A(0.32) H36B(0.32) H36C(0.32)
5.a Ternary CH refined with riding coordinates:
 N2(H2), N3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B),
 C21(H21A,H21B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B)
5.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C22(H22), C38(H38), C40(H40), C42(H42), C46(H46), C48(H48),
 C50(H50), C54(H54), C56(H56), C58(H58), C62(H62), C64(H64), C66(H66)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_olex2_submission_special_instructions 'No special instructions were received'