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_4514768
_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         'C33 H51 N2 O Zn, C2 F6 N O4 S2'
_chemical_formula_sum            'C35 H51 F6 N3 O5 S2 Zn'
_chemical_formula_weight         837.27
_chemical_name_systematic        '7DiPPZn(H)(THF) NTf2'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-01-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6599(3)
_cell_length_b                   14.2563(3)
_cell_length_c                   20.5882(5)
_cell_measurement_reflns_used    5196
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      26.0210
_cell_measurement_theta_min      3.2860
_cell_volume                     4009.34(16)
_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_environment      N~2~
_diffrn_ambient_temperature      150.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1428
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.905
_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    -34.00  47.00   1.00   17.50    --  -18.62  77.00 -30.00   81
  2  \w    -49.00 -23.00   1.00   17.50    --  -18.62  77.00-180.00   26
  3  \w      1.00  42.00   1.00   17.50    --  -18.62  77.00-180.00   41
  4  \w      0.00  80.00   1.00   17.50    --   20.10  77.00  30.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0393095000
_diffrn_orient_matrix_UB_12      0.0319257000
_diffrn_orient_matrix_UB_13      -0.0042217000
_diffrn_orient_matrix_UB_21      0.0315595000
_diffrn_orient_matrix_UB_22      -0.0378905000
_diffrn_orient_matrix_UB_23      -0.0077422000
_diffrn_orient_matrix_UB_31      -0.0122637000
_diffrn_orient_matrix_UB_32      0.0047700000
_diffrn_orient_matrix_UB_33      -0.0333181000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0958
_diffrn_reflns_av_unetI/netI     0.0983
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18404
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.865
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.005
_diffrn_reflns_theta_min         2.858
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.787
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             1752
_exptl_crystal_preparation
'Reaction of 7DiPPZnPh(NTf2) with HBPin in oDCB'
_exptl_crystal_recrystallization_method
'Grown from THF solution layered with pentane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.537
_refine_diff_density_min         -0.619
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 2021 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     520
_refine_ls_number_reflns         9222
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0625
_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^)+(0.0692P)^2^+0.3047P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1538
_refine_ls_wR_factor_ref         0.1787
_reflns_Friedel_coverage         0.734
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.816
_reflns_number_gt                6916
_reflns_number_total             9222
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01370_si_006.cif
_cod_data_source_block           amji431
_cod_database_code               4514768
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C31H43N3O4F6S2Zn(C4H8O)
_chemical_oxdiff_usercomment     'RP560 7DiPPZn(H)(THF) NTf2 '
_reflns_odcompleteness_completeness 99.78
_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. Others
 Sof(O4)=Sof(O5)=1-FVAR(1)
 Sof(O6)=Sof(O7)=FVAR(1)
 Sof(F5)=1-FVAR(2)
 Sof(F7)=FVAR(2)
 Sof(N4)=1-FVAR(3)
 Sof(N3)=FVAR(3)
3.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C33(H33A,H33B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22)
3.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C)
;
_shelx_res_checksum              42783
_shelx_hkl_checksum              43431
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.478
_oxdiff_exptl_absorpt_empirical_full_min 0.754