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_1529347
_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 H56 B F3 Ir N O2 P2, C6 H5 F'
_chemical_formula_sum            'C47 H61 B F4 Ir N O2 P2'
_chemical_formula_weight         1012.91
_chemical_name_systematic        (PNP)Ir(pi-alkynylboronate)
_chemical_properties_physical
'Air-sensitive, Moisture-sensitive, Oxygen-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-03-11
_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                90
_cell_angle_beta                 107.160(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.781(5)
_cell_length_b                   26.065(9)
_cell_length_c                   12.544(5)
_cell_measurement_reflns_used    787
_cell_measurement_temperature    110.15
_cell_measurement_theta_max      49.77
_cell_measurement_theta_min      3.56
_cell_volume                     4618(3)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v6.45A (Bruker, 2003)'
_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 0.827
_diffrn_measured_fraction_theta_max 0.995
_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  0.1556
_diffrn_reflns_av_unetI/netI     0.1229
_diffrn_reflns_laue_measured_fraction_full 0.827
_diffrn_reflns_laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            35126
_diffrn_reflns_point_group_measured_fraction_full 0.827
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         60.430
_diffrn_reflns_theta_min         3.129
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.691
_exptl_absorpt_correction_T_max  0.7518
_exptl_absorpt_correction_T_min  0.5339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1090 before and 0.0758 after correction.
The Ratio of minimum to maximum transmission is 0.7102.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_description       block
_exptl_crystal_F_000             2056
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.808
_refine_diff_density_min         -1.554
_refine_diff_density_rms         0.183
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         6914
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0662
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0523P)^2^+41.2165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1512
_refine_ls_wR_factor_ref         0.1707
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4844
_reflns_number_total             6914
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc02161h4.cif
_cod_data_source_block           oz419
_cod_depositor_comments
'Adding full bibliography for 1529345--1529348.cif.'
_cod_database_code               1529347
_audit_block_doi                 10.5517/cc13258m
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.477
_shelx_estimated_absorpt_t_min   0.308
_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. Restrained distances
 F3A-C35A \\sim F3-C35 \\sim F2A-C35A \\sim F2-C35 \\sim F1A-C35A \\sim F1-C35
 with sigma of 0.005
 C35A-C32 \\sim C35-C32
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C1S) = Uanis(C2S) = Uanis(C3S) = Uanis(C4S) = Uanis(C5S) = Uanis(C6S)
Uanis(F2) = Uanis(F3) = Uanis(F1)
Uanis(C35) = Uanis(C35A)
Uanis(F1) = Uanis(F2) = Uanis(F3) = Uanis(F1A) = Uanis(F2A) = Uanis(F3A)
4. Others
 Sof(C35A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(C35)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21), C24(H24)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C10(H10), C12(H12), C13(H13), C30(H30), C31(H31),
 C33(H33), C34(H34), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S)
5.c Fitted hexagon refined as free rotating group:
 C1S(C2S,C3S,C4S,C5S,C6S)
5.d Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), 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),
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              27795
_shelx_hkl_checksum              40257