Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes
Lee, Chun-I; DeMott, Jessica C.; Pell, Christopher J.; Christopher, Alyson; Zhou, Jia; Bhuvanesh, Nattamai; Ozerov, Oleg V.; Chem. Sci. 6 (2015) 6572–; doi:10.1039/C5SC02161H

data_1529345
_publ_section_title
;
 Ligand survey results in identification of PNP pincer complexes of
 iridium as long-lived and chemoselective catalysts for dehydrogenative
 borylation of terminal alkynes
;
_journal_issue                   11
_journal_name_full               'Chem. Sci.'
_journal_page_first              6572
_journal_paper_doi               10.1039/C5SC02161H
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C41 H59 B Ir N O2 P2'
_chemical_formula_sum            'C41 H59 B Ir N O2 P2'
_chemical_formula_weight         862.84
_chemical_name_systematic        (PNP)Ir=C=C(4-Me-C6H4)(Bpin)
_chemical_properties_physical
'Air-sensitive, Moisture-sensitive, Oxygen-sensitive'
_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             2013-12-18
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_audit_update_record
;
2014-07-19 deposited with the CCDC.
2015-08-04 downloaded from the CCDC.
;
_cell_angle_alpha                66.601(2)
_cell_angle_beta                 89.641(2)
_cell_angle_gamma                87.421(2)
_cell_formula_units_Z            4
_cell_length_a                   14.2754(5)
_cell_length_b                   16.7152(6)
_cell_length_c                   18.3801(7)
_cell_measurement_reflns_used    9948
_cell_measurement_temperature    110.15
_cell_measurement_theta_max      60.864
_cell_measurement_theta_min      2.619
_cell_volume                     4020.7(3)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      110.15
_diffrn_measured_fraction_theta_full 0.826
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0626
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_laue_measured_fraction_full 0.826
_diffrn_reflns_laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            95613
_diffrn_reflns_point_group_measured_fraction_full 0.826
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         60.948
_diffrn_reflns_theta_min         2.620
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.432
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.5477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0888 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.7284.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: fluorobenzene, pentane'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.666
_refine_diff_density_min         -0.710
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     876
_refine_ls_number_reflns         11999
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0258
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0279P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0536
_refine_ls_wR_factor_ref         0.0559
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9573
_reflns_number_total             11999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc02161h4.cif
_cod_data_source_block           oz415
_cod_depositor_comments
'Adding full bibliography for 1529345--1529348.cif.'
_cod_database_code               1529345
_audit_block_doi                 10.5517/cc13256k
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.866
_shelx_estimated_absorpt_t_min   0.588
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{B1, B1A}
3. Restrained distances
 C28-B1 \\sim C28-B1A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(B1) = Uanis(O1) = Uanis(O2) = Uanis(C36) = Uanis(C37) = Uanis(C38) =
Uanis(C39) = Uanis(C40) = Uanis(C41) = Uanis(B1A) = Uanis(O1A) = Uanis(O2A) =
Uanis(C36A) = Uanis(C37A) = Uanis(C38A) = Uanis(C39A) = Uanis(C40A) =
Uanis(C41A)
5. Same fragment restrains
{B1, O1, O2, C36, C37, C38, C39, C40, C41}
as
{B1A, O1A, O2A, C36A, C37A, C38A, C39A, C40A, C41A}
6. Others
 Sof(B1A)=Sof(O1A)=Sof(O2A)=Sof(C36A)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=
 Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39A)=Sof(C40A)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(1)
 Sof(B1)=Sof(O1)=Sof(O2)=Sof(C36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21), C24(H24), C15B(H15B), C18B(H18B), C21B(H21B),
 C24B(H24B)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C30(H30), C31(H31),
 C33(H33), C34(H34), C2B(H2B), C4B(H4B), C5B(H5B), C9B(H9B), C10B(H10B),
 C12B(H12B), C30B(H30B), C31B(H31B), C33B(H33B), C34B(H34B)
7.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C37A(H37D,H37E,H37F), C38A(H38D,H38E,H38F), C40A(H40D,H40E,H40F),
 C41A(H41D,H41E,H41F), C7B(H7BA,H7BB,H7BC), C14B(H14D,H14E,H14F), C16B(H16D,
 H16E,H16F), C17B(H17D,H17E,H17F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F),
 C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F), C25B(H25D,H25E,H25F), C26B(H26D,
 H26E,H26F), C35B(H35D,H35E,H35F), C37B(H37G,H37H,H37I), C38B(H38G,H38H,H38I),
 C40B(H40G,H40H,H40I), C41B(H41G,H41H,H41I)
;
_shelx_res_checksum              22659
_shelx_hkl_checksum              55807