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_1564840
_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_formula_moiety         'C33 H43 B Ir N P2, 0.5(C7 H8)'
_chemical_formula_sum            'C36.5 H47 B Ir N P2'
_chemical_formula_weight         764.70
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2020-06-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-07-06 deposited with the CCDC.	2021-10-04 downloaded from the CCDC.
;
_cell_angle_alpha                117.239(2)
_cell_angle_beta                 90.452(2)
_cell_angle_gamma                92.091(2)
_cell_formula_units_Z            4
_cell_length_a                   11.8373(4)
_cell_length_b                   17.7095(6)
_cell_length_c                   18.0512(6)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      33.995
_cell_measurement_theta_min      2.670
_cell_volume                     3361.0(2)
_computing_cell_refinement
'SAINT V8.38 Bruker AXS Inc., Madison, WI, USA.'
_computing_data_reduction
'SAINT V8.38 Bruker AXS Inc., Madison, WI, USA.'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0471
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_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       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            149950
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.269
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.094
_exptl_absorpt_correction_T_max  0.2740
_exptl_absorpt_correction_T_min  0.1458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1055 before and 0.0571 after correction. The Ratio of minimum to maximum transmission is 0.5321. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.511
_exptl_crystal_description       plate
_exptl_crystal_F_000             1540
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene, pentane'
_exptl_crystal_size_max          0.528
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.633
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     783
_refine_ls_number_reflns         15415
_refine_ls_number_restraints     122
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0248
_refine_ls_R_factor_gt           0.0183
_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^)+(0.0130P)^2^+3.7637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0382
_refine_ls_wR_factor_ref         0.0411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13528
_reflns_number_total             15415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01850g3.cif
_cod_data_source_block           yhc228
_cod_original_formula_sum        'C36.50 H47 B Ir N P2'
_cod_database_code               1564840
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.221
_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 Ir(H) groups
2. Restrained distances
 P4-C64A \\sim P4-C64
 with sigma of 0.02
 C65A-C64A \\sim C66-C64 \\sim C66A-C64A \\sim C65-C64
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A
 with sigma of 0.02
 P4-C65 \\sim P4-C66 \\sim P4-C65A \\sim P4-C66A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P4 \\sim C64 \\sim C65 \\sim C66 \\sim C64A \\sim C65A \\sim C66A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C66A) = Uanis(C65)
Uanis(C65A) = Uanis(C66)
4. Rigid body (RIGU) restrains
 P4, C64, C65, C66, C64A, C65A, C66A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66A)=
 Sof(H66D)=Sof(H66E)=Sof(H66F)=1-FVAR(1)
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=FVAR(1)
6.a Riding coordinates:
 Ir1(H), Ir2(HA)
6.b Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C28(H28), C31(H31), C55(H55), C58(H58), C61(H61),
 C64(H64), C64A(H64A)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C18(H18), C19(H19), C20(H20), C21(H21), C35(H35), C36(H36), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C51(H51), C52(H52), C53(H53), C54(H54), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S),
  C6S(H6S)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C65A(H65D,H65E,H65F), C66A(H66D,H66E,H66F),
 C7S(H7SA,H7SB,H7SC)
;
_shelx_res_checksum              81610
_shelx_hkl_checksum              36651
_olex2_submission_special_instructions 'No special instructions were received'