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_4518120
_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         'C44 H34 Cl3 Ga N4 P2 Rh', 'Ga Cl4'
_chemical_formula_sum            'C88 H68 Cl14 Ga4 N8 P4 Rh2'
_chemical_formula_weight         2342.38
_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     direct
_atom_sites_solution_secondary   difmap
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_cell_angle_alpha                102.6042(10)
_cell_angle_beta                 96.8135(10)
_cell_angle_gamma                92.8749(9)
_cell_formula_units_Z            2
_cell_length_a                   16.4861(2)
_cell_length_b                   17.1218(2)
_cell_length_c                   18.1159(2)
_cell_measurement_reflns_used    35355
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.4740
_cell_measurement_theta_min      2.9250
_cell_volume                     4939.85(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
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_computing_molecular_graphics    Yadokari-XG
_computing_publication_material  Yadokari-XG
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    SIR-2014
_diffrn_ambient_temperature      123(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Rigaku (Mo) X-ray Source'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            82573
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         2.775
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    1.892
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.546
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       prism
_exptl_crystal_F_000             2328
_exptl_crystal_size_max          0.510
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.050
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_refine_diff_density_min         -1.150
_refine_diff_density_rms         0.174
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.231
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1296
_refine_ls_number_reflns         20167
_refine_ls_number_restraints     107
_refine_ls_restrained_S_all      1.238
_refine_ls_R_factor_all          0.1090
_refine_ls_R_factor_gt           0.0988
_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^)+91.8789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2187
_refine_ls_wR_factor_ref         0.2224
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17468
_reflns_number_total             20167
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02779_si_002.cif
_cod_data_source_block           2-Ga
_cod_depositor_comments
'Adding full bibliography for 4518119--4518122.cif.'
_cod_original_cell_volume        4939.84(10)
_cod_database_code               4518120
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.445
_shelx_estimated_absorpt_t_max   0.911
_shelx_res_checksum              89903
_shelx_hkl_checksum              44475
_shelx_fab_checksum              4360