Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand
Takaya, Jun; Ogawa, Koki; Nakaya, Ryota; Iwasawa, Nobuharu; ACS Catalysis 10 (2020) 12223–12228; doi:10.1021/acscatal.0c02779

data_4518122
_publ_section_title
;
 Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine
 Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand
;
_journal_issue                   20
_journal_name_full               'ACS Catalysis'
_journal_page_first              12223
_journal_page_last               12228
_journal_paper_doi               10.1021/acscatal.0c02779
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety
'C57 H45 N3 P2 Ga Rh Cl2', 'Ga Cl4', 'C4 H10 O', 'C2 O0.5'
_chemical_formula_sum            'C126 H110 Cl12 Ga4 N6 O3 P6 Rh2'
_chemical_formula_weight         2852.11
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90.5378(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.41790(10)
_cell_length_b                   14.68540(10)
_cell_length_c                   22.68860(10)
_cell_measurement_reflns_used    56597
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      76.2170
_cell_measurement_theta_min      3.7450
_cell_volume                     12466.76(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    Yadokari-XG
_computing_publication_material  Yadokari-XG
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            76878
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.380
_diffrn_reflns_theta_min         3.233
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    6.573
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70934
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       prism
_exptl_crystal_F_000             5760
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.050
_refine_diff_density_max         1.384
_refine_diff_density_min         -0.958
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     764
_refine_ls_number_reflns         12691
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0488P)^2^+26.1387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0900
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12203
_reflns_number_total             12691
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02779_si_002.cif
_cod_data_source_block           GaRhHCl-10
_cod_depositor_comments
'Adding full bibliography for 4518119--4518122.cif.'
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4518122
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.506
_shelx_estimated_absorpt_t_max   0.735
_shelx_res_checksum              31233
_shelx_hkl_checksum              34786