C‒H Borylation Catalysis of Heteroaromatics by a Rhenium Boryl Polyhydride
Donnelly, Liam J.; Faber, Teresa; Morrison, Carole A.; Nichol, Gary S.; Thomas, Stephen P.; Love, Jason B.; ACS Catalysis 11 (2021) 7394–7400; doi:10.1021/acscatal.1c00869

data_4518792
_publ_section_title
;
 C--H Borylation Catalysis of Heteroaromatics by a Rhenium Boryl
 Polyhydride
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              7394
_journal_page_last               7400
_journal_paper_doi               10.1021/acscatal.1c00869
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C45 H67 B K O8 P2 Re'
_chemical_formula_sum            'C45 H67 B K O8 P2 Re'
_chemical_formula_weight         1034.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)

_shelx_SHELXL_version_number      2018/3

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.
Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
Sheldrick, G.M. (2015). Acta Cryst. C71, 3-8.

_publ_contact_author_address      'University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ' 
_publ_contact_author_email        'jason.love@ed.ac.uk, Stephen.Thomas@ed.ac.uk'
_publ_contact_author_name         'Liam J. Donnelly, Teresa Faber, Carole A. Morrison, Stephen P. Thomas* and Jason B. Love*'
_publ_contact_author_fax          ?
_publ_contact_author_phone        ?
_publ_requested_journal           ?
_publ_section_title               'The Synthesis and Structure of a Rhenium Boryl Polyhydride Catalyst for the C-H Borylation of Heteroaromatics'
_publ_section_abstract            'Transition metal complexes bearing metal-boron bonds are of particular relevance to catalytic C-H borylation reactions, with iridium polyboryl and polyhydrido-boryl complexes the current benchmark catalysts for these transformations. Herein, we demonstrate that polyhydride boryl phosphine rhenium complexes are accessible and catalyze the C-H boryla-tion of heteraromatic substrates.  Reaction of [K(DME)(18-c-6)][ReH4(Bpin)(eta2-HBpin)(kappa2-H2Bpin)] 1 with 1,3-bis(diphenylphosphino)propane (dppp) produced [K(DME)(18-c-6)][ReH4(eta2-HBpin)(dppp)] 2 through substitution of two equivalents of HBpin and the subsequent protonation of 2 formed the neutral complex [ReH6(Bpin)(dppp)] 3. Com-bined X-ray crystallographic and DFT studies show that 2 is best described as a sigam-borane complex, whereas 3 is a boryl complex.  Significantly, the boryl complex 2 acted as a catalyst for the C(sp2)-H borylation of a variety of heteroarenes and displayed similar reactivity to the iridium analogues.'
;
_cell_angle_alpha                90
_cell_angle_beta                 102.8880(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9998(2)
_cell_length_b                   29.3027(4)
_cell_length_c                   14.5738(2)
_cell_measurement_reflns_used    50539
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      32.1300
_cell_measurement_theta_min      3.6400
_cell_volume                     5411.73(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -41.00  49.00   0.50   10.00    --   27.51 -57.00 -60.00  180
  2  \w    -19.00  72.00   0.50   10.00    --   27.51-104.00  67.00  182
  3  \w    -20.00  69.00   0.50   10.00    --   27.51 -99.00-180.00  178
  4  \w    -20.00  69.00   0.50   10.00    --   27.51 -99.00 -90.00  178
  5  \w      6.00  96.00   0.50   10.00    --   27.51  57.00-180.00  180
  6  \w    -45.00  72.00   0.50   10.00    --   27.51 -19.00   0.00  234
  7  \w      6.00  96.00   0.50   10.00    --   27.51  57.00 -60.00  180
  8  \w      6.00  96.00   0.50   10.00    --   27.51  57.00  90.00  180
  9  \w      6.00  96.00   0.50   10.00    --   27.51  57.00-120.00  180
 10  \w    -41.00  49.00   0.50   10.00    --   27.51 -57.00 150.00  180
 11  \w      6.00  96.00   0.50   10.00    --   27.51  57.00  30.00  180
 12  \w    -95.00  -5.00   0.50   10.00    --  -25.95 -57.00  30.00  180
 13  \w      2.00  50.00   0.50   10.00    --   27.51  37.00 150.00   96
 14  \w      6.00  96.00   0.50   10.00    --   27.51  57.00   0.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0006201000
_diffrn_orient_matrix_UB_12      0.0111662000
_diffrn_orient_matrix_UB_13      0.0433070000
_diffrn_orient_matrix_UB_21      0.0172836000
_diffrn_orient_matrix_UB_22      -0.0204735000
_diffrn_orient_matrix_UB_23      0.0246296000
_diffrn_orient_matrix_UB_31      0.0532373000
_diffrn_orient_matrix_UB_32      0.0065108000
_diffrn_orient_matrix_UB_33      0.0032162000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            112966
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         3.289
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.424
_exptl_absorpt_correction_T_max  0.760
_exptl_absorpt_correction_T_min  0.601
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             2120
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.266
_exptl_crystal_size_min          0.163
_refine_diff_density_max         1.113
_refine_diff_density_min         -0.601
_refine_diff_density_rms         0.073
_refine_ls_extinction_coef       0.00012(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     548
_refine_ls_number_reflns         9895
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.151
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0208P)^2^+10.3571P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0633
_refine_ls_wR_factor_ref         0.0637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9611
_reflns_number_total             9895
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00869_si_003.cif
_cod_data_source_block           j2005
_cod_depositor_comments
'Adding full bibliography for 4518791--4518793.cif.'
_cod_database_code               4518792
_chemical_oxdiff_formula         'Re1 K1 P2 C100 H100 O20'
_chemical_oxdiff_usercomment     'J2005 '
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
The hydrides were placed in placed in positions based on the difference synthesis and refined with free uiso.

Residual electron density from disordered lattice solvent was removed from the structure using the solvent mask feature of Olex2 (98 electrons/unit cell), rendering the lattice
solvent identified as 2 molecules of hexane per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              88815
_shelx_hkl_checksum              56924
_shelx_fab_checksum              28055
_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 1.054
_oxdiff_exptl_absorpt_empirical_full_min 0.939