Low-Coordinate NHC‒Zinc Hydride Complexes Catalyze Alkyne C‒H Borylation and Hydroboration Using Pinacolborane
Procter, Richard J.; Uzelac, Marina; Cid, Jessica; Rushworth, Philip J.; Ingleson, Michael J.; ACS Catalysis 9 (2019) 5760–; doi:10.1021/acscatal.9b01370

data_4514769
_publ_section_title
;
 Low-Coordinate NHC--Zinc Hydride Complexes Catalyze Alkyne C--H
 Borylation and Hydroboration Using Pinacolborane
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              5760
_journal_paper_doi               10.1021/acscatal.9b01370
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C37 H47 F6 N3 O4 S2 Zn'
_chemical_formula_sum            'C37 H47 F6 N3 O4 S2 Zn'
_chemical_formula_weight         841.26
_chemical_name_systematic        7DiPPZnPhNTf2
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.975(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.3499(9)
_cell_length_b                   20.6938(7)
_cell_length_c                   20.4521(10)
_cell_measurement_reflns_used    12416
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      28.9980
_cell_measurement_theta_min      3.6630
_cell_volume                     7873.2(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1636
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.862
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -39.00  65.00   1.00   21.94    --  -12.00  19.00 -30.00  104
  2  \w    -25.00   6.00   1.00   21.94    --  -12.00 -99.00  30.00   31
  3  \w    -41.00  50.00   1.00   21.94    --  -12.00  57.00-150.00   91
  4  \w    -77.00 -51.00   1.00   21.94    --   11.54 178.00 -60.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0343662000
_diffrn_orient_matrix_UB_12      0.0140841000
_diffrn_orient_matrix_UB_13      0.0138179000
_diffrn_orient_matrix_UB_21      0.0063338000
_diffrn_orient_matrix_UB_22      -0.0009349000
_diffrn_orient_matrix_UB_23      -0.0325158000
_diffrn_orient_matrix_UB_31      -0.0152841000
_diffrn_orient_matrix_UB_32      0.0312433000
_diffrn_orient_matrix_UB_33      -0.0072175000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0456
_diffrn_reflns_av_unetI/netI     0.0671
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52973
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.437
_diffrn_reflns_theta_min         3.311
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.800
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89636
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       block
_exptl_crystal_F_000             3504
_exptl_crystal_preparation       'Protonation of 7DiPPZnPh2'
_exptl_crystal_recrystallization_method
'Grown from solution in ortho-dichlorobenzene layered with pentane'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.723
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     971
_refine_ls_number_reflns         18791
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0609P)^2^+2.0934P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1181
_refine_ls_wR_factor_ref         0.1419
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12111
_reflns_number_total             18791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01370_si_008.cif
_cod_data_source_block           omji268
_cod_database_code               4514769
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C37H47ZnNS2O4F6
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C12(H12), C24(H24), C24A(H24A), C15(H15), C12A(H12A), C27(H27), C27A(H27A),
 C15A(H15A)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5a,H5b), C2(H2a,H2b), C2A(H2Aa,H2Ab), C3A(H3Aa,H3Ab), C5A(H5Aa,H5Ab),
 C3(H3a,H3b), C4(H4a,H4b), C4A(H4Aa,H4Ab)
2.c Aromatic/amide H refined with riding coordinates:
 C22A(H22A), C10(H10), C8(H8), C22(H22), C21A(H21A), C35(H35), C20A(H20A),
 C20(H20), C31(H31), C9(H9), C21(H21), C10A(H10A), C35A(H35A), C8A(H8A),
 C31A(H31A), C32(H32), C34(H34), C9A(H9A), C33(H33), C32A(H32A), C33A(H33A),
 C34A(H34A)
2.d Idealised Me refined as rotating group:
 C26A(H26d,H26e,H26f), C13(H13a,H13b,H13c), C25(H25a,H25b,H25c), C14(H14a,H14b,
 H14c), C28A(H28d,H28e,H28f), C16(H16a,H16b,H16c), C29(H29a,H29b,H29c),
 C17(H17a,H17b,H17c), C25A(H25d,H25e,H25f), C26(H26a,H26b,H26c), C28(H28a,H28b,
 H28c), C13A(H13d,H13e,H13f), C29A(H29d,H29e,H29f), C17A(H17d,H17e,H17f),
 C14A(H14d,H14e,H14f), C16A(H16d,H16e,H16f)
;
_shelx_res_checksum              33530
_shelx_hkl_checksum              4176
_olex2_date_sample_data_collection 2016-09-22
_olex2_submission_original_sample_id omji268
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.109
_oxdiff_exptl_absorpt_empirical_full_min 0.922