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_4518793
_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         'C33 H44 B O2 P2 Re, C7 H8'
_chemical_formula_sum            'C40 H52 B O2 P2 Re'
_chemical_formula_weight         823.76
_chemical_name_systematic        ReH6(dppp)(Bpin)
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-10
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.5282(3)
_cell_length_b                   24.9634(8)
_cell_length_c                   26.1194(9)
_cell_measurement_reflns_used    18194
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      29.3810
_cell_measurement_theta_min      3.6790
_cell_volume                     7516.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.924
_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    -15.00  31.00   1.00   30.00    --   -9.35 -99.00 142.00   46
  2  \w    -15.00  51.00   1.00   30.00    --   10.76 -99.00 142.00   66
  3  \w    -41.00  21.00   1.00   30.00    --   -9.35  77.00-150.00   62
  4  \w    -12.00  83.00   1.00   30.00    --   10.76  38.00  90.00   95
  5  \w    -26.00  25.00   1.00   30.00    --   10.76 -77.00-120.00   51
  6  \w    -21.00   6.00   1.00   30.00    --   10.76 -77.00 -90.00   27
  7  \w    -41.00   7.00   1.00   30.00    --   10.76 -77.00  90.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0127966000
_diffrn_orient_matrix_UB_12      -0.0259008000
_diffrn_orient_matrix_UB_13      -0.0095921000
_diffrn_orient_matrix_UB_21      0.0228730000
_diffrn_orient_matrix_UB_22      -0.0074149000
_diffrn_orient_matrix_UB_23      0.0242003000
_diffrn_orient_matrix_UB_31      -0.0556876000
_diffrn_orient_matrix_UB_32      -0.0090020000
_diffrn_orient_matrix_UB_33      0.0077289000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0687
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            81541
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.788
_diffrn_reflns_theta_min         3.356
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.351
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.456
_exptl_crystal_description       rod
_exptl_crystal_F_000             3344
_exptl_crystal_size_max          0.503
_exptl_crystal_size_mid          0.079
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.901
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         9931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0067P)^2^+8.0152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0503
_refine_ls_wR_factor_ref         0.0541
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7948
_reflns_number_total             9931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00869_si_004.cif
_cod_data_source_block           jl20005_refinalized
_cod_depositor_comments
'Adding full bibliography for 4518791--4518793.cif.'
_cod_database_code               4518793
_chemical_oxdiff_formula         'C40 H47 B1 O2 P2 Re1'
_chemical_oxdiff_usercomment     '@ 120 K LD668'
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;

The hydrides were placed in placed in positions based on the difference synthesis and refined with free uiso.

;
_shelx_res_checksum              80847
_shelx_hkl_checksum              87773
_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 5.031
_oxdiff_exptl_absorpt_empirical_full_min 0.625