Catalytic Activation of Remote Alkenes through Silyl-Rhodium(III) Complexes
Prieto-Pascual, Unai; Martínez de Morentin, Aitor; Choquesillo-Lazarte, Duane; Rodríguez Diéguez, Antonio; Freixa, Zoraida; Huertos, Miguel A. A.; Dalton Transactions  (2023) –; doi:10.1039/D3DT00624G

data_7713216
_publ_section_title
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 Catalytic Activation of Remote Alkenes through Silyl-Rhodium(III)
 Complexes
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_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00624G
_journal_year                    2023
_chemical_formula_moiety         '1(C48 H44 N1 P2 Rh1 Si1), C32 H12 B F24'
_chemical_formula_sum            'C80 H57 B F24 N P2 Rh Si'
_chemical_formula_weight         1692.01
_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   geom
_audit_creation_date             2023-05-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
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2023-05-25 deposited with the CCDC.	2023-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                114.646(3)
_cell_angle_beta                 100.541(3)
_cell_angle_gamma                104.702(3)
_cell_formula_units_Z            2
_cell_length_a                   14.6909(13)
_cell_length_b                   17.0539(14)
_cell_length_c                   17.9179(16)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.475
_cell_measurement_theta_min      2.318
_cell_volume                     3727.6(6)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker Apex4, 2022'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0774
_diffrn_reflns_av_unetI/netI     0.0693
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            105227
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.602
_diffrn_reflns_theta_min         1.991
_exptl_absorpt_coefficient_mu    0.394
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6767
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1160 before and 0.0683 after correction.
The Ratio of minimum to maximum transmission is 0.9070.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       block
_exptl_crystal_F_000             1708
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.674
_refine_diff_density_min         -1.100
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1357
_refine_ls_number_reflns         22656
_refine_ls_number_restraints     513
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0569
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0810P)^2^+3.0400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1433
_refine_ls_wR_factor_ref         0.1611
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16568
_reflns_number_total             22656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00624g2.cif
_cod_data_source_block           2_l2
_cod_database_code               7713216
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.962
_olex2_refinement_description
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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
 C64-F22A \\sim C64-F22B
 with sigma of 0.02
 F24A-C64 \\sim F24B-C64
 with sigma of 0.02
 F23A-C64 \\sim F23B-C64
 with sigma of 0.02
 Rh1B-N1B \\sim Rh1A-N1A
 with sigma of 0.02
 Rh1B-Si1B \\sim Rh1A-Si1A
 with sigma of 0.02
 Rh1B-P3B \\sim Rh1A-P3A
 with sigma of 0.02
 Rh1B-P1B \\sim Rh1A-P1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C34A) = Uanis(C34B)
Uanis(C41A) = Uanis(C41B)
Uanis(C29A) = Uanis(C29B)
Uanis(C4A) = Uanis(C4B)
Uanis(C33A) = Uanis(C33B)
Uanis(P1A) = Uanis(P1B)
Uanis(C40A) = Uanis(C40B)
Uanis(C30A) = Uanis(C30B)
4. Rigid body (RIGU) restrains
 C35B, Rh1B, N1B, P1B, Si1B, P3B, C19B, C23B, C13B, C7B, C1B, C24B, C25B, C26B,
  C31B, C43B, C37B, C30B, C20B, C22B, C18B, C14B, C8B, C12B, C2B, C6B, C27B,
 C36B, C32B, C48B, C44B, C42B, C38B, C21B, C29B, C17B, C15B, C9B, C11B, C3B,
 C5B, C28B, C33B, C47B, C45B, C41B, C39B, C16B, C10B, C4B, C34B, C46B, C40B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F24A, C64, F23A, F22A, C63
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C63, C64, F23B, F22B, F24B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.01
 F1, C56, F2, F3, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Rh1B)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(N1B)=Sof(C19B)=
 Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(C22B)=Sof(C23B)=Sof(C24B)=
 Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(Si1B)=
 Sof(C25B)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(P1B)=Sof(C13B)=Sof(C18B)=Sof(H18B)=
 Sof(C17B)=Sof(H17B)=Sof(C16B)=Sof(H16B)=Sof(C15B)=Sof(H15B)=Sof(C14B)=
 Sof(H14B)=Sof(C7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=
 Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=Sof(P3B)=Sof(C43B)=Sof(C48B)=Sof(H48B)=
 Sof(C47B)=Sof(H47B)=Sof(C46B)=Sof(H46B)=Sof(C45B)=Sof(H45B)=Sof(C44B)=
 Sof(H44B)=Sof(C31B)=Sof(C36B)=Sof(H36B)=Sof(C35B)=Sof(H35B)=Sof(C34B)=
 Sof(H34B)=Sof(C33B)=Sof(H33B)=Sof(C32B)=Sof(H32B)=Sof(C37B)=Sof(C42B)=
 Sof(H42B)=Sof(C41B)=Sof(H41B)=Sof(C40B)=Sof(H40B)=Sof(C39B)=Sof(H39B)=
 Sof(C38B)=Sof(H38B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=
 Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=
 Sof(H26F)=1-FVAR(1)
 Sof(Rh1A)=Sof(P3A)=Sof(P1A)=Sof(Si1A)=Sof(N1A)=Sof(C43A)=Sof(C42A)=Sof(H42A)=
 Sof(C6A)=Sof(H6A)=Sof(C31A)=Sof(C41A)=Sof(H41A)=Sof(C13A)=Sof(C37A)=Sof(C7A)=
 Sof(C48A)=Sof(H48A)=Sof(C1A)=Sof(C44A)=Sof(H44A)=Sof(C5A)=Sof(H5A)=Sof(C12A)=
 Sof(H12A)=Sof(C19A)=Sof(C18A)=Sof(H18A)=Sof(C40A)=Sof(H40A)=Sof(C46A)=
 Sof(H46A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C4A)=Sof(H4A)=Sof(C32A)=
 Sof(H32A)=Sof(C45A)=Sof(H45A)=Sof(C39A)=Sof(H39A)=Sof(C24A)=Sof(C36A)=
 Sof(H36A)=Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C38A)=Sof(H38A)=
 Sof(C20A)=Sof(H20A)=Sof(C23A)=Sof(C2A)=Sof(H2A)=Sof(C8A)=Sof(H8A)=Sof(C47A)=
 Sof(H47A)=Sof(C34A)=Sof(H34A)=Sof(C10A)=Sof(H10A)=Sof(C33A)=Sof(H33A)=
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C14A)=Sof(H14A)=Sof(C17A)=
 Sof(H17A)=Sof(C35A)=Sof(H35A)=Sof(C21A)=Sof(H21A)=Sof(C11A)=Sof(H11A)=
 Sof(C27A)=Sof(H27A)=Sof(C9A)=Sof(H9A)=Sof(C3A)=Sof(H3A)=Sof(C22A)=Sof(C29A)=
 Sof(H29A)=Sof(C28A)=Sof(H28A)=Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=FVAR(1)
 Sof(F23B)=Sof(F22B)=Sof(F24B)=1-FVAR(2)
 Sof(F24A)=Sof(F23A)=Sof(F22A)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C42A(H42A), C6A(H6A), C41A(H41A), C81(H81), C67(H67), C57(H57), C51(H51),
 C48A(H48A), C59(H59), C73(H73), C70(H70), C44A(H44A), C5A(H5A), C12A(H12A),
 C62(H62), C18A(H18A), C75(H75), C40A(H40A), C54(H54), C65(H65), C78(H78),
 C46A(H46A), C4A(H4A), C32A(H32A), C45A(H45A), C39A(H39A), C36A(H36A),
 C38A(H38A), C20A(H20A), C2A(H2A), C8A(H8A), C47A(H47A), C34A(H34A), C10A(H10A),
  C33A(H33A), C14A(H14A), C17A(H17A), C35A(H35A), C21A(H21A), C11A(H11A),
 C27A(H27A), C9A(H9A), C3A(H3A), C29A(H29A), C28A(H28A), C16A(H16A), C15A(H15A),
  C20B(H20B), C21B(H21B), C27B(H27B), C28B(H28B), C29B(H29B), C18B(H18B),
 C17B(H17B), C16B(H16B), C15B(H15B), C14B(H14B), C8B(H8B), C9B(H9B), C10B(H10B),
  C11B(H11B), C12B(H12B), C48B(H48B), C47B(H47B), C46B(H46B), C45B(H45B),
 C44B(H44B), C36B(H36B), C35B(H35B), C34B(H34B), C33B(H33B), C32B(H32B),
 C42B(H42B), C41B(H41B), C40B(H40B), C39B(H39B), C38B(H38B), C2B(H2B), C3B(H3B),
  C4B(H4B), C5B(H5B), C6B(H6B)
6.b Fitted hexagon refined as free rotating group:
 C13B(C18B,C17B,C16B,C15B,C14B), C7B(C8B,C9B,C10B,C11B,C12B), C43B(C48B,C47B,
 C46B,C45B,C44B), C31B(C36B,C35B,C34B,C33B,C32B), C37B(C42B,C41B,C40B,C39B,
 C38B), C1B(C2B,C3B,C4B,C5B,C6B)
6.c Naphthalene refined as free rotating group:
 N1B(C19B,C20B,C21B,C22B,C23B,C24B,C27B,C28B,C29B)
6.d Idealised Me refined with riding coordinates:
 C30B(H30D,H30E,H30F), C25B(H25D,H25E,H25F)
6.e Idealised Me refined as rotating group:
 C26A(H26A,H26B,H26C), C25A(H25A,H25B,H25C), C30A(H30A,H30B,H30C), C26B(H26D,
 H26E,H26F)
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_shelx_res_checksum              881
_shelx_hkl_checksum              27393
_olex2_submission_special_instructions 'No special instructions were received'