Unexpected B/Al Transelementation within a Rh Pincer Complex.
Lai, Qingheng; Bhuvanesh, Nattamai; Ozerov, Oleg V.; Journal of the American Chemical Society 142 (2020) 20920–20923; doi:10.1021/jacs.0c09344

data_4135383
_publ_section_title
;
 Unexpected B/Al Transelementation within a Rh Pincer Complex.
;
_journal_issue                   50
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              20920
_journal_page_last               20923
_journal_paper_doi               10.1021/jacs.0c09344
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C22 H34 B N2 O2 P2 Rh'
_chemical_formula_sum            'C22 H34 B N2 O2 P2 Rh'
_chemical_formula_weight         534.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.369(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.210(3)
_cell_length_b                   14.684(3)
_cell_length_c                   14.725(3)
_cell_measurement_reflns_used    9959
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      25.035
_cell_measurement_theta_min      2.265
_cell_volume                     2458.6(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 2016)'
_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      110.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker PHOTON'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0550
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            26179
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.039
_diffrn_reflns_theta_max         25.039
_diffrn_reflns_theta_min         1.791
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.845
_exptl_absorpt_correction_T_max  0.4286
_exptl_absorpt_correction_T_min  0.3214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1088 before and 0.0689 after correction. The Ratio of minimum to maximum transmission is 0.7499. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.127
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.828
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.318
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     423
_refine_ls_number_reflns         4331
_refine_ls_number_restraints     861
_refine_ls_restrained_S_all      1.215
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0472
_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^)+13.3057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1068
_refine_ls_wR_factor_ref         0.1086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3952
_reflns_number_total             4331
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09344_si_002.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 4135382--4135384.cif.'
_cod_original_cell_volume        2458.5(10)
_cod_database_code               4135383
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.846
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-C19 \\sim C20-C18
 with sigma of 0.005
 N2A-B1 \\sim N2-B1
 with sigma of 0.005
 P1-C9A \\sim P1-C9 \\sim P1-C12 \\sim P1-C12A \\sim P2-C18A \\sim P2-C18 \\sim
P2-C15A \\sim P2-C15
 with sigma of 0.005
 C20A-C18A \\sim C20-C18 \\sim C19A-C18A \\sim C19-C18 \\sim C17A-C15A \\sim
C17-C15 \\sim C16A-C15A ~
 C16-C15 \\sim C13-C12 \\sim C13A-C12A \\sim C14A-C12A \\sim C14-C12 \\sim
C9-C10 \\sim C9A-C10A \\sim C9-
 C11 \\sim C9A-C11A
 with sigma of 0.005
 C10-C11 \\sim C10A-C11A \\sim C13-C14 \\sim C13A-C14A \\sim C16-C17 \\sim
C16A-C17A \\sim C19-C20 ~
 C19A-C20A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
N2 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim N2A \\sim C5A \\sim C6A \\sim C7A
\\sim C8A: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
P1 \\sim P2 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C9A \\sim C10A
\\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A
\\sim C18A \\sim C19A \\sim C20A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(N2) = Uanis(N2A)
Uanis(C11A) = Uanis(C11)
Uanis(C19A) = Uanis(C19)
4. Rigid body (RIGU) restrains
 N2, C5, C6, C7, C8, N2A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 P1, P2, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C9A, C10A,
 C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Same fragment restrains
{N1, C1, C2, C3, C4} sigma for 1-2: 0.005, 1-3: 0.04
as
{N2, C5, C6, C7, C8}
{N1, C1, C2, C3, C4} sigma for 1-2: 0.005, 1-3: 0.04
as
{N2A, C5A, C6A, C7A, C8A}
6. Others
 Sof(N2A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15A)=
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(N2)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C9)=
 Sof(H9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=
 Sof(H11C)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12), C15(H15), C18(H18), C9A(H9A), C12A(H12A), C15A(H15A),
 C18A(H18A)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C5A(H5A), C6A(H6A), C7A(H7A)
7.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,
 H20B,H20C), C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C13A(H13D,H13E,H13F),
 C14A(H14D,H14E,H14F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C19A(H19D,
 H19E,H19F), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              48288
_shelx_hkl_checksum              82266
_olex2_submission_special_instructions 'No special instructions were received'