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_4518791
_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         '2(C27 H30 P2 Re)'
_chemical_formula_sum            'C54 H60 P4 Re2'
_chemical_formula_weight         1205.30
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-05
_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, 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                85.9370(10)
_cell_angle_beta                 85.1180(10)
_cell_angle_gamma                71.918(2)
_cell_formula_units_Z            2
_cell_length_a                   9.38140(10)
_cell_length_b                   12.2395(2)
_cell_length_c                   21.7629(3)
_cell_measurement_reflns_used    40767
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      32.7700
_cell_measurement_theta_min      3.5640
_cell_volume                     2364.26(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (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_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 0.998
_diffrn_measured_fraction_theta_max 0.932
_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    -59.00  -8.00   1.00   10.00    --  -17.52 102.00-159.00   51
  2  \w    -14.00  61.00   1.00   10.00    --   19.09-102.00  97.00   75
  3  \w    -42.00  14.00   1.00   10.00    --  -17.52 -77.00  90.00   56
  4  \w     -8.00  89.00   1.00   10.00    --   19.09  57.00   0.00   97
  5  \w     -8.00  89.00   1.00   10.00    --   19.09  57.00  30.00   97
  6  \w    -18.00  98.00   1.00   10.00    --   19.09  19.00-120.00  116
  7  \w    -51.00  46.00   1.00   10.00    --   19.09 -57.00  90.00   97
  8  \w     -3.00  92.00   1.00   10.00    --   19.09  38.00 120.00   95
  9  \w    -15.00  59.00   1.00   10.00    --   19.09 -99.00-180.00   74
 10  \w     -8.00  89.00   1.00   10.00    --   19.09  57.00-120.00   97
 11  \w    -51.00  46.00   1.00   10.00    --   19.09 -57.00-120.00   97
 12  \w      2.00  73.00   1.00   10.00    --   20.00-121.00  46.54   71
 13  \w    -42.00  14.00   1.00   10.00    --  -17.52 -77.00-120.00   56
 14  \w    -42.00  14.00   1.00   10.00    --  -17.52 -77.00-150.00   56
 15  \w    -92.00 -42.00   1.00   10.00    --  -17.52 153.00-166.32   50
 16  \w    -18.00  46.00   1.00   10.00    --   19.09  19.00 -60.00   64
 17  \w     39.00 106.00   1.00   10.00    --   19.09 178.00  60.00   67
 18  \w      4.00  73.00   1.00   10.00    --   19.09-123.00 -72.72   69
 19  \w      9.00  78.00   1.00   10.00    --   19.09-131.00 -22.97   69
 20  \w      2.00  73.00   1.00   10.00    --   20.00-121.00 134.16   71
 21  \w      8.00  77.00   1.00   10.00    --   20.00-128.00-111.80   69
;
_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      -0.0126655000
_diffrn_orient_matrix_UB_12      0.0320029000
_diffrn_orient_matrix_UB_13      0.0269410000
_diffrn_orient_matrix_UB_21      -0.0473010000
_diffrn_orient_matrix_UB_22      0.0483274000
_diffrn_orient_matrix_UB_23      -0.0160595000
_diffrn_orient_matrix_UB_31      -0.0628978000
_diffrn_orient_matrix_UB_32      -0.0191031000
_diffrn_orient_matrix_UB_33      0.0094145000
_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  0.0741
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            121195
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.357
_diffrn_reflns_theta_min         3.206
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.287
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70415
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_density_diffrn    1.693
_exptl_crystal_description       prism
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.277
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.188
_refine_diff_density_min         -1.261
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     638
_refine_ls_number_reflns         17093
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.175
_refine_ls_R_factor_all          0.0549
_refine_ls_R_factor_gt           0.0421
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0162P)^2^+3.1456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0720
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14694
_reflns_number_total             17093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00869_si_002.cif
_cod_data_source_block           jl20009_refinalized
_cod_depositor_comments
'Adding full bibliography for 4518791--4518793.cif.'
_cod_database_code               4518791
_chemical_oxdiff_formula         'C162 H174 P12 Re2 '
_chemical_oxdiff_usercomment     '@ 120 K LD705.3'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;

A phenyl substituent on the DPPP ligand coordinated to Re1 (C(22), C(23), C(24), C(25), C(26), 
C(27), C(22A), C(23A), C(24A), C(25A), C(26A), C(27A)) was positionally disordered over two positions. 
As a result, the ring was split and refined with an occupany ratio of 0.540:0.460.

The central propyl carbon of the DPPP ligand bound to Re2 (C(41), C(41A)) was positionally disorder over two positions. 
As a result, C(41) was split and refined with an occupancy ratio of 0.405:0.595.   

The hydrides were placed in placed in positions based on the difference synthesis and refined with free uiso. 
The Re-H distance for terminal hydrides (H1, H2, H5, H6) were restrained to a distance of 1.47 A within the standard uncertainty 
of 0.01 through the use of DFIX command. The Re-H distance for bridging hydrides (H3, H4, H7, H8) were restrained to a distance 
of 1.95 A within the standard uncertainty of 0.01 through the use of DFIX command. The interatomic distances between bridging hydrides
(H3 and H4, H7 and H8) were restrained to a distance of 2.1 A within the standard uncertainty of 0.01 through the use of DANG command.

;
_shelx_res_checksum              45879
_shelx_hkl_checksum              55033
_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 3.136
_oxdiff_exptl_absorpt_empirical_full_min 0.538