Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of Ynamides.
Debrauwer, Vincent; Turlik, Aneta; Rummler, Lénaic; Prescimone, Alessandro; Blanchard, Nicolas; Houk, K. N.; Bizet, Vincent; Journal of the American Chemical Society 142 (2020) 11153–11164; doi:10.1021/jacs.0c03556

data_4135062
_publ_section_title
;
 Ligand-Controlled Regiodivergent Palladium-Catalyzed Hydrogermylation of
 Ynamides.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11153
_journal_page_last               11164
_journal_paper_doi               10.1021/jacs.0c03556
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C30 H27 Ge N O3'
_chemical_formula_sum            'C30 H27 Ge N O3'
_chemical_formula_weight         522.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.01.31 svn.r88ba2a32 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.273(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.0288(8)
_cell_length_b                   14.5601(7)
_cell_length_c                   18.7951(8)
_cell_measurement_reflns_used    9907
_cell_measurement_temperature    123
_cell_volume                     4956.4(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30707
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.114
_diffrn_reflns_theta_min         2.439
_diffrn_source_current           0.6
_diffrn_source_power             0.03
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.935
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6447
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0980 before and 0.0384 after correction.
The Ratio of minimum to maximum transmission is 0.8558.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.051
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     633
_refine_ls_number_reflns         9240
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0514P)^2^+5.5802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1034
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8195
_reflns_number_total             9240
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03556_si_005.cif
_cod_data_source_block           dt0075_123k_0ma
_cod_depositor_comments
'Adding full bibliography for 4135061--4135063.cif.'
_cod_database_code               4135062
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.710
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C32(H32A,H32B), C3(H3A,H3B), C2(H2A,H2B)
2.b Aromatic/amide H refined with riding coordinates:
 C38(H38), C35(H35), C44(H44), C50(H50), C48(H48), C45(H45), C37(H37),
 C40(H40), C53(H53), C54(H54), C41(H41), C20(H20), C51(H51), C52(H52), C8(H8),
 C46(H46), C47(H47), C23(H23), C10(H10), C14(H14), C21(H21), C56(H56), C26(H26),
  C24(H24), C22(H22), C7(H7), C11(H11), C5(H5), C60(H60), C18(H18), C28(H28),
 C27(H27), C15(H15), C30(H30), C57(H57), C29(H29), C59(H59), C16(H16), C58(H58),
  C17(H17)
2.c Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              59308
_shelx_hkl_checksum              92554
_olex2_date_sample_data_collection 2016-06-29
_olex2_date_sample_submission    2016-04-26
_olex2_submission_original_sample_id DT0075_123K
_olex2_submission_special_instructions 'No special instructions were received'