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_4123233
_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         'C24 H44 B2 N6 O2 P Rh'
_chemical_formula_sum            'C24 H44 B2 N6 O2 P Rh'
_chemical_formula_weight         604.15
_chemical_name_systematic
;
 ?
;
_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     iterative
_audit_creation_date             2014-02-20
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Olex2 1.2
(compiled 2014.02.11 svn.r2872 for OlexSys, GUI svn.r4767)
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_cell_angle_alpha                90
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_cell_length_b                   10.660(2)
_cell_length_c                   21.4520(5)
_cell_measurement_reflns_used    6208
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.8415
_cell_measurement_theta_min      3.0198
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_computing_cell_refinement
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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
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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
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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)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.0
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.837
_diffrn_measurement_details
;
  1 omega   16.00   43.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9830   77.0000  -30.0000 27

  2 omega   -5.00   81.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3111   77.0000 -150.0000 86

  3 omega   -9.00   76.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3111   77.0000   90.0000 85
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0134040000
_diffrn_orient_matrix_UB_12      -0.0012427000
_diffrn_orient_matrix_UB_13      0.0321935000
_diffrn_orient_matrix_UB_21      0.0202561000
_diffrn_orient_matrix_UB_22      -0.0366022000
_diffrn_orient_matrix_UB_23      -0.0087018000
_diffrn_orient_matrix_UB_31      0.0136379000
_diffrn_orient_matrix_UB_32      0.0556094000
_diffrn_orient_matrix_UB_33      -0.0050432000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.837
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11082
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.837
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.902
_diffrn_reflns_theta_min         3.069
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97160
_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    1.379
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2528
_exptl_crystal_size_max          0.1907
_exptl_crystal_size_mid          0.1155
_exptl_crystal_size_min          0.0445
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5832
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0252P)^2^+5.6696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0699
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5072
_reflns_number_total             5832
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5113172_si_002.cif
_cod_data_source_block           rnp1102
_cod_depositor_comments
'Adding full bibliography for 4123232--4123234.cif.'
_cod_original_cell_volume        5819.4(12)
_cod_database_code               4123233
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C24H44B2N6O2P Rh'
_chemical_oxdiff_usercomment     'Barby`s TpRhBH'
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C2A, C2}
{O2, O2A}
3. Restrained distances
 O1-C1 \\sim O1A-C1A \\sim O2-C2 \\sim O2-C2A
 with sigma of 0.02
 C1-C3 \\sim C1-C4 \\sim C1A-C3A \\sim C1A-C4A \\sim C2-C5 \\sim C2-C6 \\sim
C2A-C5A \\sim C2A-C6A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C2A) = Uanis(C2)
Uanis(O2) = Uanis(O2A)
Uanis(C1) = Uanis(C1A)
Uiso(C3A) = Uiso(C4A) = Uiso(C5A) = Uiso(C6A)
5. Others
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=
 Sof(H6AB)=Sof(H6AC)=Sof(O1A)=Sof(O2A)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=
 Sof(H4C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(O1)=Sof(O2)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 B2(H2)
6.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C17(H17), C22(H22)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C3A(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC),
 C5(H5A,H5B,H5C), C5A(H5AA,H5AB,H5AC), C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC),
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C24(H24A,H24B,H24C)
;
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_shelx_hkl_checksum              33328
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'