Toward anti-Markovnikov 1-Alkyne O-Phosphoramidation: Exploiting Metal-Ligand Cooperativity in a 1,3-N,O-Chelated Cp*Ir(III) Complex.
Drover, Marcus W.; Love, Jennifer A.; Schafer, Laurel L.; Journal of the American Chemical Society 138 (2016) 8396–8399; doi:10.1021/jacs.6b05143

data_4130615
_publ_section_title
;
 Toward anti-Markovnikov 1-Alkyne O-Phosphoramidation: Exploiting
 Metal-Ligand Cooperativity in a 1,3-N,O-Chelated Cp*Ir(III) Complex.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8396
_journal_page_last               8399
_journal_paper_doi               10.1021/jacs.6b05143
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C34 H48 Ir N O3 P, C32 H12 B F24'
_chemical_formula_sum            'C66 H60 B F24 Ir N O3 P'
_chemical_formula_weight         1605.13
_chemical_name_systematic        'iridium vinyloxy 2'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-05
_audit_creation_method
;
Olex2 1.2
(compiled Feb 16 2016 13:09:46 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.808(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1931(14)
_cell_length_b                   20.3353(17)
_cell_length_c                   19.7277(16)
_cell_measurement_reflns_used    9845
_cell_measurement_temperature    90
_cell_measurement_theta_max      29.146
_cell_measurement_theta_min      2.474
_cell_volume                     6796.5(10)
_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
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device
'Bruker-Nonius APEXII CCD area detector and D8 diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            103575
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.457
_diffrn_reflns_theta_max         25.457
_diffrn_reflns_theta_min         1.449
_exptl_absorpt_coefficient_mu    2.099
_exptl_absorpt_correction_T_max  0.7773
_exptl_absorpt_correction_T_min  0.4382
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;  
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.569
_exptl_crystal_description       prism
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.959
_refine_diff_density_min         -1.096
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         12525
_refine_ls_number_restraints     1518
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0695
_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^)+(0.0102P)^2^+62.5512P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1305
_refine_ls_wR_factor_ref         0.1476
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9999
_reflns_number_total             12525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b05143_si_002.cif
_cod_data_source_block           jl218_may4
_cod_database_code               4130615
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F7-C49 \\sim F9-C49 \\sim F9A-C49A \\sim F8A-C49A \\sim F8-C49 \\sim F7A-C49A
 with sigma of 0.02
 C16A-C15A \\sim C16-C15
 with sigma of 0.02
 C14-C13A \\sim C14A-C13
 with sigma of 0.02
 O2-C13 \\sim O2-C13A
 with sigma of 0.02
 C14-C13A \\sim C14A-C13
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim
C33 \\sim C34: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim C30A \\sim C31A \\sim
C32A \\sim C33A \\sim C34A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(C25A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C27A) \\sim Ueq,
Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C30A) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C33A) \\sim Ueq,
Uanis(C34A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F9A) = Uanis(F9)
Uanis(C13A) = Uanis(C13)
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(Ir1A)=Sof(P1A)=Sof(O1A)=Sof(O3A)=Sof(N1A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=
 Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=
 Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=
 Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=
 Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(C28A)=
 Sof(C29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=
 Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(1)
 Sof(Ir1)=Sof(P1)=Sof(O1)=Sof(O3)=Sof(N1)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=
 Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=
 Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=
 Sof(H11C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(C28)=
 Sof(C29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(1)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(2)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(C49A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(C49)=FVAR(3)
6.a :
 C25(C26,C27,C28,C29,C30,C31,C32,C33,C34,Ir1A,P1A,O1A,O3A,N1A,C1A,C2A,C3A,C4A,
 C5A,C6A,C7A,C8A,C9A,C10A,C11A,C12A,C13A,C14A,C15A,C16A,C17A,C18A,C19A,C20A,
 C21A,C22A,C23A,C24A), C25A(C26A,C27A,C28A,C29A,C30A,C31A,C32A,C33A,C34A,F1,F2,
 F3,F4,F5,F6,F13,F14,F15,F16,F17,F18,F19,F20,F21,C35,C36,C37,C38,C39,C40,C41,
 C42,C43,C44,C45,C46,C47,C48,C50,C51,C52,C53,C54,C55,C56,C57,C58,C59,C60,C61,
 C62,C63,C64,C65,C66,B1,F7,F8,F9,F10,F11,F12,F22,F23,F24,C49,F7A,F8A,F9A,F10A,
 F11A,F12A,F22A,F23A,F24A,C49A)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C13A(H13C,H13D), C15A(H15C,H15D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C19(H19), C20(H20), C21(H21),
 C2A(H2A), C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C19A(H19A), C20A(H20A),
 C21A(H21A), C36(H36), C38(H38), C40(H40), C44(H44), C46(H46), C48(H48),
 C52(H52), C54(H54), C56(H56), C60(H60), C62(H62), C64(H64)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C16(H16A,H16B,H16C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C12A(H12D,
 H12E,H12F), C14A(H14D,H14E,H14F), C16A(H16D,H16E,H16F), C23A(H23D,H23E,H23F),
 C24A(H24D,H24E,H24F), C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F), C32A(H32D,
 H32E,H32F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F)
;
_shelx_res_checksum              62472
_shelx_hkl_checksum              97052
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'