Synthesis and structures of anionic rhenium polyhydride complexes of boron‒hydride ligands and their application in catalysis
Donnelly, Liam J.; Parsons, Simon; Morrison, Carole A.; Thomas, Stephen P.; Love, Jason B.; Chemical Science  (2020) –; doi:10.1039/D0SC03458D

data_1559028
_publ_section_title
;
 Synthesis and structures of anionic rhenium polyhydride complexes of
 boron--hydride ligands and their application in catalysis
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03458D
_journal_year                    2020
_chemical_formula_moiety         'C32 H64 B4 Re, C16 H34.03 K O8'
_chemical_formula_sum            'C48 H98.03 B4 K O8 Re'
_chemical_formula_weight         1071.83
_chemical_name_systematic        '[ReH8BBN4][K(18c6)(DME)]'
_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             2019-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)

_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, Simon Parsons, Gary S. Nichol, Stephen P. Thomas* and Jason B. Love*'
_publ_contact_author_fax          ?
_publ_contact_author_phone        ?
_publ_requested_journal           ?
_publ_section_title               'Synthesis and Structures of Anionic Rhenium Boryl Polyhydrides and their Catalysis'
_publ_section_abstract            'The anionic rhenium boryl hydride complex, [ReH7(Bpin)3]-, has been synthesized by exhaustive deoxygenation of perrhenate (ReO4-) with HBpin. X-ray diffraction, NMR and IR spectroscopy analysis supports its structure as a polyhydridic Re centre with trigonal planar geometry with respect to the boryl ligands. This complex was applied in the catalytic hydroboration N-heteroaromatic substrates using [NR4][ReO4] as a precatalyst and in the stoichiometric C-H borylation of arenes. The reactivity of  [ReH7(Bpin)3]- was further explored through reactions with 9-BBN or PPh3 to produce the corresponding derivatized complexes. This work represent the first example for the synthesis of Re compounds bearing boron-centred ligands in the Re(III), Re(V) and Re(VII) oxidation states.'

;
_audit_update_record
;
2020-01-21 deposited with the CCDC.	2020-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                96.7140(10)
_cell_angle_beta                 91.2900(10)
_cell_angle_gamma                102.351(2)
_cell_formula_units_Z            2
_cell_length_a                   11.2627(2)
_cell_length_b                   15.9727(3)
_cell_length_c                   16.0123(2)
_cell_measurement_reflns_used    39271
_cell_measurement_temperature    220(2)
_cell_measurement_theta_max      30.3910
_cell_measurement_theta_min      3.6110
_cell_volume                     2791.22(8)
_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 (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      220.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1042
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.923
_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   -104.00 -39.00   1.00   15.00    --  -24.15-178.00 -90.00   65
  2  \w      2.00  96.00   1.00   15.00    --   25.71  57.00 -90.00   94
  3  \w     -7.00  39.00   1.00   15.00    --   25.71  77.00 120.00   46
  4  \w     -7.00  39.00   1.00   15.00    --   25.71  77.00   0.00   46
  5  \w    -41.00 101.00   1.00   15.00    --   25.71  19.00  90.00  142
  6  \w    -20.00  71.00   1.00   15.00    --   25.71 -99.00-120.00   91
  7  \w    -45.00  49.00   1.00   15.00    --   25.71 -57.00 120.00   94
  8  \w    -39.00   9.00   1.00   15.00    --  -24.15 -77.00  30.00   48
  9  \w    -57.00  39.00   1.00   15.00    --  -24.15  77.00  30.00   96
 10  \w     35.00 108.00   1.00   15.00    --   25.71-178.00 150.00   73
 11  \w    -45.00  49.00   1.00   15.00    --   25.71 -57.00 -90.00   94
 12  \w     -7.00  39.00   1.00   15.00    --   25.71  77.00-120.00   46
 13  \w      2.00  96.00   1.00   15.00    --   25.71  57.00-180.00   94
 14  \w     -7.00  39.00   1.00   15.00    --   25.71  77.00  30.00   46
 15  \w     -7.00  39.00   1.00   15.00    --   25.71  77.00 -60.00   46
 16  \w    -20.00  15.00   1.00   15.00    --   25.71 -99.00  90.00   35
 17  \w      2.00  96.00   1.00   15.00    --   25.71  57.00 150.00   94
;
_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      -0.0468719000
_diffrn_orient_matrix_UB_12      -0.0372368000
_diffrn_orient_matrix_UB_13      0.0016483000
_diffrn_orient_matrix_UB_21      0.0434967000
_diffrn_orient_matrix_UB_22      -0.0262642000
_diffrn_orient_matrix_UB_23      -0.0039702000
_diffrn_orient_matrix_UB_31      0.0087993000
_diffrn_orient_matrix_UB_32      0.0047725000
_diffrn_orient_matrix_UB_33      0.0444494000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            73081
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.923
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.525
_diffrn_reflns_theta_min         3.326
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.296
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.942
_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            'Clear Red'
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       Block
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.354
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.737
_refine_diff_density_min         -0.696
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         15734
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0282
_refine_ls_R_factor_gt           0.0227
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0181P)^2^+0.7134P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0444
_refine_ls_wR_factor_ref         0.0461
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14293
_reflns_number_total             15734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03458d2.cif
_cod_data_source_block           j19010_refinalised
_cod_database_code               1559028
_chemical_oxdiff_formula         'Re1 B4 C100 K1 O10 H100'
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_shelx_res_checksum              4918
_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 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.865