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_4514770
_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         '0.67(C31 H43 F6 N3 O4 S2 Zn), C6 H4 Cl2'
_chemical_formula_sum            'C26.67 H32.67 Cl2 F4 N2 O2.67 S1.33 Zn0.67'
_chemical_formula_weight         657.11
_chemical_name_systematic        '[(7DiPP)Zn(H)NTf2]'
_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   mixed
_audit_creation_date             2018-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                117.002(9)
_cell_angle_beta                 106.690(6)
_cell_angle_gamma                94.539(6)
_cell_formula_units_Z            3
_cell_length_a                   10.0474(6)
_cell_length_b                   16.5268(15)
_cell_length_c                   16.5479(14)
_cell_measurement_reflns_used    4375
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      24.2690
_cell_measurement_theta_min      3.1720
_cell_volume                     2273.4(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_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      150.0(3)
_diffrn_detector_area_resol_mean 8.0714
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.887
_diffrn_measurement_details
;
  1 omega   12.00   42.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000   30.0000 30

  2 omega   -9.00   25.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -      -18.7745  -99.0000   30.0000 34

  3 omega  -20.00    5.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -      -18.7745  -99.0000  -90.0000 25

  4 omega  -16.00   23.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -      -18.7745  -99.0000  150.0000 39

  5 omega  -31.00   41.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000  150.0000 72

  6 omega  -30.00   -4.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000   30.0000 26

  7 omega  -35.00   22.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000  120.0000 57

  8 omega   -2.00   89.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245   57.0000   30.0000 91

  9 omega  -39.00   33.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000  -90.0000 72

 10 omega  -49.00   22.00   1.0000    3.9700
omega____ theta____ kappa____ phi______ frames
    -       20.0245  -57.0000 -120.0000 71
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0083844000
_diffrn_orient_matrix_UB_12      -0.0410770000
_diffrn_orient_matrix_UB_13      0.0025953000
_diffrn_orient_matrix_UB_21      -0.0280116000
_diffrn_orient_matrix_UB_22      0.0144981000
_diffrn_orient_matrix_UB_23      0.0377988000
_diffrn_orient_matrix_UB_31      -0.0702184000
_diffrn_orient_matrix_UB_32      -0.0239105000
_diffrn_orient_matrix_UB_33      -0.0351183000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1231
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24348
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.887
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.213
_diffrn_reflns_theta_min         2.689
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.875
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91657
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       block
_exptl_crystal_F_000             1018
_exptl_crystal_preparation       'Metathesis of ZnPh with HBPin'
_exptl_crystal_recrystallization_method
'Grown from a solution in orthodichlorobenzene layered with pentane at 2 C'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.986
_refine_diff_density_min         -0.652
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.942
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     539
_refine_ls_number_reflns         24348
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      0.940
_refine_ls_R_factor_all          0.1204
_refine_ls_R_factor_gt           0.0699
_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^)+(0.0850P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.1735
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13746
_reflns_number_total             24348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01370_si_002.cif
_cod_data_source_block           amji405_twin1_hklf4
_cod_database_code               4514770
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C33H43F6N3O4Zn
_chemical_oxdiff_usercomment     'RP - zinc hydride trfilimide (+ NME indole)'
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(4)
 0.377(14) 0.02(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H27 of C27, H20 of C20, H10 of C10, H12 of C12, H9 of C9,
   H33 of C33, H34 of C34, H35 of C35, H36 of C36, H21 of C21, H42 of C42, H41
  of C41, H40 of C40, H43 of C43, H15 of C15, H24 of C24, H22 of C22, H8 of C8
 At 1.5 times of:
  All C(H,H,H) groups, H of C33
3. Restrained distances
 C39-Cl3 \\sim C38-Cl4
 with sigma of 0.02
 C39-C38 \\sim C38-C43 \\sim C43-C42 \\sim C42-C41 \\sim C41-C40 \\sim C40-C39
 with sigma of 0.02
 C39-C43 \\sim C39-C41 \\sim C42-C38 \\sim C42-C40 \\sim C38-C40 \\sim C43-C41
 with sigma of 0.04
 Cl3-C40 \\sim Cl3-C38 \\sim Cl4-C39 \\sim Cl4-C43
 with sigma of 0.04
4. Restrained planarity
 Cl3, Cl4, C39, C38, C43, C42, C41, C40
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl4 \\sim C39 \\sim C38 \\sim C43 \\sim C42 \\sim C41 \\sim C40:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C41) = Uanis(C42) = Uanis(C43) = Uanis(C38) = Uanis(C39) = Uanis(C40)
6. Rigid body (RIGU) restrains
 Cl3, Cl4, C39, C38, C43, C42, C41, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: Cl3(0.5) Cl4(0.5) C43(0.5) H43(0.5) C38(0.5) C39(0.5) C40(0.5)
 H40(0.5) C41(0.5) H41(0.5) C42(0.5) H42(0.5)
8.a Ternary CH refined with riding coordinates:
 C15(H15), C24(H24), C27(H27), C12(H12)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
8.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C8(H8), C20(H20), C10(H10), C9(H9), C21(H21), C36(H36), C35(H35),
 C34(H34), C33(H33), C43(H43), C40(H40), C41(H41), C42(H42)
8.d Fitted hexagon refined as free rotating group:
 C43(C38,C39,C40,C41,C42)
8.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C13(H13A,H13B,H13C), C17(H17A,H17B,H17C), C26(H26A,H26B,
 H26C), C25(H25A,H25B,H25C), C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C16(H16A,
 H16B,H16C)
;
_shelx_res_checksum              46085
_shelx_hkl_checksum              42481
_olex2_submission_special_instructions 'No special instructions were received'