Cooperative C-H Activation of Pyridine by PBP Complexes of Rh and Ir Can Lead to Bridging 2-Pyridyls with Different Connectivity to the B-M Unit
Cao, Yihan; Shih, Wei-Chun; Bhuvanesh, Nattamai; Zhou, Jia; Ozerov, Oleg V.; Chemical Science  (2021) –; doi:10.1039/D1SC01850G

data_1564839
_publ_section_title
;
 Cooperative C-H Activation of Pyridine by PBP Complexes of Rh and Ir Can
 Lead to Bridging 2-Pyridyls with Different Connectivity to the B-M Unit
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01850G
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H40 B Br N P2 Rh'
_chemical_formula_sum            'C29 H40 B Br N P2 Rh'
_chemical_formula_weight         658.19
_chemical_name_systematic        (PBP)RhPyBr
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-07
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2020-07-06 deposited with the CCDC.	2021-10-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2163(11)
_cell_length_b                   11.2163(11)
_cell_length_c                   22.862(3)
_cell_measurement_reflns_used    9909
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.92
_cell_measurement_theta_min      2.54
_cell_volume                     2876.2(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            33592
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.624
_diffrn_reflns_theta_min         1.816
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.113
_exptl_absorpt_correction_T_max  0.4305
_exptl_absorpt_correction_T_min  0.3744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0706 before and 0.0608 after correction. The Ratio of minimum to maximum transmission is 0.870. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.222
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.182
_refine_diff_density_max         0.346
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 2812 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         6682
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0243
_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^)+(0.0133P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0464
_refine_ls_wR_factor_ref         0.0478
_reflns_Friedel_coverage         0.949
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                6185
_reflns_number_total             6682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01850g3.cif
_cod_data_source_block           yhc072
_cod_original_cell_volume        2876.2(7)
_cod_database_code               1564839
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.700
_shelx_estimated_absorpt_t_min   0.651
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C28A-C27A \\sim C28-C27 \\sim C29-C27A \\sim C29-C27
 with sigma of 0.005
 P2-C27A \\sim P2-C27
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
P2 \\sim C27 \\sim C27A \\sim C28 \\sim C28A \\sim C29: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 P2, C27, C27A, C28, C28A, C29
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=1-FVAR(1)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C21(H21), C24(H24), C27(H27), C27A(H27A)
6.b Me refined with riding coordinates:
 C29(H29A,H29B,H29C), C29(H29D,H29E,H29F)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16)
6.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C),
 C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              67137
_shelx_hkl_checksum              85681
_olex2_submission_special_instructions 'No special instructions were received'