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_7043191
_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         'C32 H12 B F24, C20 H35 Cl0.22 Ir N2'
_chemical_formula_sum            'C52 H47 B Cl0.22 F24 Ir N2'
_chemical_formula_weight         1366.72
_chemical_name_systematic        iridium(imine)6-membered
_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
_audit_creation_date             2017-03-09
_audit_creation_method
;
Olex2 1.2
(compiled Mar  2 2017 14:02:25 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-03-09 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                93.337(2)
_cell_angle_beta                 110.084(2)
_cell_angle_gamma                103.367(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7608(13)
_cell_length_b                   13.3680(15)
_cell_length_c                   17.2480(18)
_cell_measurement_reflns_used    9349
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      29.113
_cell_measurement_theta_min      2.507
_cell_volume                     2657.8(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    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      90(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Apex Duo II'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            51623
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.169
_diffrn_reflns_theta_min         1.272
_exptl_absorpt_coefficient_mu    2.646
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.5479
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0830 before and 0.0421 after correction.
The Ratio of minimum to maximum transmission is 0.7346.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.708
_exptl_crystal_description       plate
_exptl_crystal_F_000             1349
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.967
_refine_diff_density_min         -1.029
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1008
_refine_ls_number_reflns         14303
_refine_ls_number_restraints     1666
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0443
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0597P)^2^+6.0865P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1145
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12165
_reflns_number_total             14303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01499f2.cif
_cod_data_source_block           mo_jl211_0m_a
_cod_database_code               7043191
_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 C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Ir-Ir01
 -0.35 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1
 with sigma of 0.01
 F19-C52 \\sim F20-C52 \\sim F21-C52
 with sigma of 0.01
 C20A-C19A \\sim C19A-C18C \\sim C18C-C17 \\sim C17-C16
 with sigma of 0.01
 C13A-C14A \\sim C14A-C15A
 with sigma of 0.02
 C17A-C16A \\sim C18A-C17A \\sim C19-C18A \\sim C20-C19
 with sigma of 0.01
 F4-C28 \\sim F5-C28 \\sim F6-C28
 with sigma of 0.02
 F2-C27 \\sim F2A-C27 \\sim F1-C27 \\sim F1A-C27 \\sim F3A-C27 \\sim F3-C27
 with sigma of 0.01
 F8-C36 \\sim F8A-C36 \\sim F9-C36 \\sim F9A-C36 \\sim F7-C36 \\sim F7A-C36
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 F14-C43 \\sim F14A-C43 \\sim F15-C43 \\sim F15A-C43 \\sim F13-C43 \\sim
F13A-C43
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.01
 C51-F22 \\sim C51-F23 \\sim C51-F24 \\sim C51A-F22A \\sim C51A-F23A \\sim
C51A-F24A
 with sigma of 0.01
 C13-C14 \\sim C12-C13 \\sim C11-C12
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A
\\sim C8A \\sim C9A \\sim C10A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
F9 \\sim F9A \\sim F7 \\sim F7A \\sim F8 \\sim F8A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
F9A \\sim F9: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F8A \\sim F8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim
Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(F8) \\sim Ueq, Uanis(F8A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(Ir) = Uanis(Ir01)
Uanis(C45) = Uanis(C45A)
Uanis(C51A) = Uanis(C51)
Uanis(C50) = Uanis(C50A)
Uanis(C49) = Uanis(C49A)
Uanis(C48A) = Uanis(C48)
Uanis(C52) = Uanis(C52A)
Uanis(C7A) = Uanis(C7)
4. 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
5. Others
 Sof(Ir)=Sof(H2)=1-FVAR(1)
 Sof(H1)=Sof(Ir01)=FVAR(1)
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
 Sof(C45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(C48)=Sof(H48)=Sof(C49A)=Sof(C50A)=
 Sof(H50A)=Sof(F23A)=Sof(F24A)=Sof(C51A)=Sof(F19A)=Sof(F21A)=Sof(F20A)=
 Sof(C52A)=Sof(F22A)=1-FVAR(5)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(C45)=Sof(C46)=
 Sof(H46)=Sof(C47)=Sof(C48A)=Sof(H48A)=Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=
 Sof(C52)=FVAR(5)
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=1-FVAR(6)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(6)
 Sof(H12C)=Sof(H12D)=Sof(C15A)=Sof(H15C)=Sof(C14A)=Sof(H14C)=Sof(H14D)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C19)=Sof(H19A)=
 Sof(H19B)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C18A)=Sof(H18A)=Sof(H18B)=
 Sof(C17A)=Sof(H17C)=Sof(H17D)=1-FVAR(7)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H12A)=Sof(H12B)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C18C)=
 Sof(H18C)=Sof(H18D)=FVAR(7)
6.a :
 C1(C2,C3,C4,C5,C6,C7,C8,C9,C10), C1A(C2A,C3A,C4A,C5A,C6A,C7A,C8A,C9A,C10A)
6.b Ternary CH refined with riding coordinates:
 N1(H1), N2(H2)
6.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C12(H12C,H12D), C12(H12A,
 H12B), C14(H14A,H14B), C14A(H14C,H14D), C13A(H13C,H13D), C20(H20A,H20B),
 C17(H17A,H17B), C19(H19A,H19B), C16A(H16A,H16B), C20A(H20C,H20D), C18A(H18A,
 H18B), C17A(H17C,H17D), C19A(H19C,H19D), C18C(H18C,H18D)
6.d Aromatic/amide H refined with riding coordinates:
 C22(H22), C24(H24), C26(H26), C30(H30), C32(H32), C34(H34), C38(H38),
 C40(H40), C42(H42), C46(H46), C48A(H48A), C50(H50), C46A(H46A), C48(H48),
 C50A(H50A), C15A(H15C), C16(H16)
6.e Fitted hexagon refined as free rotating group:
 C45(C46,C47,C48A,C49,C50), C45A(C46A,C47A,C48,C49A,C50A)
6.f Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC),
 C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F)
;
_olex2_submission_special_instructions 'No special instructions were received'