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_4514774
_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         'C41 H57 N2 O2 Zn, C2 F6 N O4 S2'
_chemical_formula_sum            'C43 H57 F6 N3 O6 S2 Zn'
_chemical_formula_weight         954.39
_chemical_name_systematic        '[IDiPPZnPh(THF)2][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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                95.505(3)
_cell_angle_beta                 100.925(3)
_cell_angle_gamma                110.249(3)
_cell_formula_units_Z            2
_cell_length_a                   11.9544(4)
_cell_length_b                   13.4764(5)
_cell_length_c                   15.7416(5)
_cell_measurement_reflns_used    6520
_cell_measurement_temperature    149.9(3)
_cell_measurement_theta_max      26.1390
_cell_measurement_theta_min      3.1110
_cell_volume                     2299.96(15)
_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      149.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.855
_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    -17.00  18.00   1.00    4.50    --  -18.77 -99.00-180.00   35
  2  \w    -39.00  47.00   1.00    4.50    --  -18.77  57.00  90.00   86
  3  \w    -68.00  12.00   1.00    4.50    --  -18.77 -77.00 -30.00   80
  4  \w    -19.00  42.00   1.00    4.50    --   20.02 -99.00-120.00   61
  5  \w     -1.00  89.00   1.00    4.50    --   20.02  57.00 -30.00   90
  6  \w    -51.00   4.00   1.00    4.50    --   20.02 -77.00-150.00   55
  7  \w     35.00  98.00   1.00    4.50    --   20.02-178.00-150.00   63
;
_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      0.0214286000
_diffrn_orient_matrix_UB_12      0.0424566000
_diffrn_orient_matrix_UB_13      -0.0233783000
_diffrn_orient_matrix_UB_21      -0.0120593000
_diffrn_orient_matrix_UB_22      -0.0380052000
_diffrn_orient_matrix_UB_23      -0.0382888000
_diffrn_orient_matrix_UB_31      -0.0603010000
_diffrn_orient_matrix_UB_32      -0.0002486000
_diffrn_orient_matrix_UB_33      -0.0126565000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0731
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.855
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21430
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.084
_diffrn_reflns_theta_min         2.677
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57068
_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    1.378
_exptl_crystal_description       block
_exptl_crystal_F_000             998
_exptl_crystal_recrystallization_method 'THF solution layered with pentane'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.566
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     586
_refine_ls_number_reflns         10556
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0495P)^2^+0.9659P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1180
_refine_ls_wR_factor_ref         0.1343
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7855
_reflns_number_total             10556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01370_si_003.cif
_cod_data_source_block           amji416
_cod_original_cell_volume        2299.96(14)
_cod_database_code               4514774
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C35H41N3OS2F6Zn
_chemical_oxdiff_usercomment     'RP534 xtals'
_reflns_odcompleteness_completeness 99.87
_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. Uiso/Uaniso restraints and constraints
Uanis(O8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 S3, O7, O8
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
4. Others
 Sof(S3)=Sof(O7)=Sof(O8)=1-FVAR(1)
 Sof(S2)=Sof(O5)=Sof(O6)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
5.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C29(H29), C30(H30), C31(H31), C32(H32), C33(H33)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              86783
_shelx_hkl_checksum              70148
_olex2_date_sample_data_collection 2018-06-05
_olex2_submission_original_sample_id '[(IDiPP)Zn(Ph)(THF)2][NTf2]'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.616
_oxdiff_exptl_absorpt_empirical_full_min 0.480