Activation of B-H, Si-H, and C-F Bonds with Tp'Rh(PMe3) Complexes: Kinetics, Mechanism, and Selectivity.
Procacci, Barbara; Jiao, Yunzhe; Evans, Meagan E.; Jones, William D.; Perutz, Robin N.; Whitwood, Adrian C.; Journal of the American Chemical Society 137 (2015) 1258–1272; doi:10.1021/ja5113172

data_4123232
_publ_section_title
;
 Activation of B-H, Si-H, and C-F Bonds with Tp'Rh(PMe3) Complexes:
 Kinetics, Mechanism, and Selectivity.
;
_journal_issue                   3
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1258
_journal_page_last               1272
_journal_paper_doi               10.1021/ja5113172
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C23 H31 B F5 N7 P Rh, F H, C5 F5 N'
_chemical_formula_sum            'C28 H32 B F11 N8 P Rh'
_chemical_formula_weight         834.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2014-03-18
_audit_creation_method
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  Olex2 1.1
  (compiled 2011.02.15 svn.r1672, GUI svn.r3494)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.322(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   34.3584(13)
_cell_length_b                   8.5376(3)
_cell_length_c                   22.8054(9)
_cell_measurement_reflns_used    8038
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      29.9667
_cell_measurement_theta_min      3.1057
_cell_volume                     6601.3(4)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -72.00  -31.00   1.0000  140.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.9830  -37.0000 -150.0000 41

  2 omega  -55.00    7.00   1.0000  140.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.9830  109.0000  -89.0000 62

  3 omega   28.00   83.00   1.0000  140.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3892   37.0000 -180.0000 55

  4 omega   -1.00   62.00   1.0000  140.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3892 -109.0000   89.0000 63
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0148759000
_diffrn_orient_matrix_UB_12      0.0515710000
_diffrn_orient_matrix_UB_13      -0.0138104000
_diffrn_orient_matrix_UB_21      0.0140302000
_diffrn_orient_matrix_UB_22      0.0615008000
_diffrn_orient_matrix_UB_23      0.0019547000
_diffrn_orient_matrix_UB_31      0.0044577000
_diffrn_orient_matrix_UB_32      -0.0210658000
_diffrn_orient_matrix_UB_33      -0.0282912000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            16475
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_min         3.112
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.663
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
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    1.679
_exptl_crystal_description       needle
_exptl_crystal_F_000             3360
_exptl_crystal_recrystallization_method pentafluoropyridine
_exptl_crystal_size_max          0.2119
_exptl_crystal_size_mid          0.0729
_exptl_crystal_size_min          0.0352
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.951
_refine_diff_density_rms         0.081
_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     463
_refine_ls_number_reflns         9556
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0303P)^2^+10.5538P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0785
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8127
_reflns_number_total             9556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5113172_si_002.cif
_cod_data_source_block           rnp1101
_cod_depositor_comments
'Adding full bibliography for 4123232--4123234.cif.'
_cod_database_code               4123232
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C23 H31 B F5 N7 P Rh'
_chemical_oxdiff_usercomment     'Barby's TpRhPMe3F'
_reflns_odcompleteness_completeness 98.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All F(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F6-H6
 0.925 with sigma of 0.001
3.a Ternary CH refined with riding coordinates:
 B1(H1)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C13(H13), C18(H18)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              5258
_shelx_hkl_checksum              86219
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'