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_4514772
_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         'C29 H42 Cl2 N2 Zn, 1.5(C4 H8 O)'
_chemical_formula_sum            'C35 H54 Cl2 N2 O1.5 Zn'
_chemical_formula_weight         663.07
_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     direct
_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                90
_cell_angle_beta                 133.379(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9149(9)
_cell_length_b                   19.5194(6)
_cell_length_c                   19.2829(13)
_cell_measurement_reflns_used    4795
_cell_measurement_temperature    150.03(10)
_cell_measurement_theta_max      28.7100
_cell_measurement_theta_min      3.4400
_cell_volume                     3533.1(8)
_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      150.03(10)
_diffrn_detector_area_resol_mean 8.0714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.846
_diffrn_measurement_details
;
  1 omega   -2.00   85.00   1.0000    3.2250
omega____ theta____ kappa____ phi______ frames
    -       18.8601   57.0000   60.0000 87

  2 omega   35.00   65.00   1.0000    3.2250
omega____ theta____ kappa____ phi______ frames
    -       18.8601  178.0000  -90.0000 30

  3 omega  -18.00   16.00   1.0000    3.2250
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -99.0000  150.0000 34

  4 omega  -48.00   23.00   1.0000    3.2250
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -57.0000  -90.0000 71
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0722728000
_diffrn_orient_matrix_UB_12      0.0094324000
_diffrn_orient_matrix_UB_13      0.0380064000
_diffrn_orient_matrix_UB_21      0.0037767000
_diffrn_orient_matrix_UB_22      0.0105978000
_diffrn_orient_matrix_UB_23      -0.0334284000
_diffrn_orient_matrix_UB_31      -0.0215930000
_diffrn_orient_matrix_UB_32      0.0334429000
_diffrn_orient_matrix_UB_33      -0.0001394000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0332
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.846
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16038
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.846
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.144
_diffrn_reflns_theta_min         3.324
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.876
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64738
_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    1.247
_exptl_crystal_description       block
_exptl_crystal_F_000             1416
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.400
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         8060
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0361P)^2^+0.5327P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0894
_refine_ls_wR_factor_ref         0.1012
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5877
_reflns_number_total             8060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01370_si_004.cif
_cod_data_source_block           amji353
_cod_original_cell_volume        3533.2(6)
_cod_original_formula_sum        'C35 H54 Cl2 N2 O1.50 Zn'
_cod_database_code               4514772
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Zn1Cl2N2C13H15
_chemical_oxdiff_usercomment     RP154
_reflns_odcompleteness_completeness 99.73
_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. Rigid body (RIGU) restrains
 O1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: O1(0.5) C2(0.5) H2A(0.5) H2B(0.5) C3(0.5) H3A(0.5) H3B(0.5)
 C4(0.5) H4A(0.5) H4B(0.5) C5(0.5) H5A(0.5) H5B(0.5)
4.a Ternary CH refined with riding coordinates:
 C00F(H00F), C00K(H00K), C00N(H00N), C00T(H00W)
4.b Secondary CH2 refined with riding coordinates:
 C00G(H00A,H00B), C00J(H00C,H00D), C00O(H00G,H00H), C00S(H00U,H00V), C00W(H1AA,
 HC), C00Z(H2AA,HH), C010(H01G,H01H), C013(H01I,H01J), C2(H2A,H2B), C3(H3A,H3B),
  C4(H4A,H4B), C5(H5A,H5B)
4.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00E(H00E), C00I(H00I), C00L(H00L), C00M(H00M), C00P(H00P)
4.d Idealised Me refined as rotating group:
 C00Q(H00J,H00O,H00Q), C00R(H00R,H00S,H00T), C00U(H00X,H00Y,H), C00V(H00Z,HA,
 HB), C00X(H00,HD,HE), C00Y(H0AA,HF,HG), C011(H01A,H01B,H01C), C012(H01D,H01E,
 H01F)
;
_shelx_res_checksum              59961
_shelx_hkl_checksum              42235
_olex2_date_sample_data_collection 2016-07-19
_olex2_submission_special_instructions 'No special instructions were received'