Palladacycle-Phosphine Catalyzed Methylation of Amines and Ketones Using Methanol.
Mamidala, Ramesh; Biswal, Priyabrata; Subramani, M. Siva; Samser, Shaikh; Venkatasubbaiah, Krishnan; The Journal of organic chemistry 84 (2019) 10472–10480; doi:10.1021/acs.joc.9b00983

data_4034014
_publ_section_title
;
 Palladacycle-Phosphine Catalyzed Methylation of Amines and Ketones Using
 Methanol.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10472
_journal_page_last               10480
_journal_paper_doi               10.1021/acs.joc.9b00983
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C50 H32 F12 N4 O4 Pd2, 2(C H2 Cl2), C H Cl2'
_chemical_formula_sum            'C53 H37 Cl6 F12 N4 O4 Pd2'
_chemical_formula_weight         1447.36
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2017-03-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                114.873(2)
_cell_angle_beta                 96.893(3)
_cell_angle_gamma                94.600(3)
_cell_formula_units_Z            2
_cell_length_a                   12.6732(14)
_cell_length_b                   15.4639(7)
_cell_length_c                   16.0509(8)
_cell_measurement_reflns_used    9980
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.19
_cell_measurement_theta_min      2.65
_cell_volume                     2803.2(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            45908
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.385
_diffrn_reflns_theta_min         1.975
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.016
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0969 before and 0.0484 after correction.
The Ratio of minimum to maximum transmission is 0.6913.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.715
_exptl_crystal_description       block
_exptl_crystal_F_000             1434
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.433
_refine_diff_density_min         -1.727
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         13761
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0471P)^2^+6.9444P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1044
_refine_ls_wR_factor_ref         0.1124
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11345
_reflns_number_total             13761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00983_si_003.cif
_cod_data_source_block           kv
_cod_database_code               4034014
_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. Others
 Fixed Sof: F11A(0.5) F10(0.5) F12(0.5) F10A(0.5) F11(0.5) F12A(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C47(H47A,H47B)
3.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C28(H28), C13(H13), C37(H37), C14(H14), C17(H17), C40(H40),
 C35(H35), C19(H19), C2(H2), C31(H31), C44(H44), C36(H36), C21(H21), C11(H11),
 C7(H7), C15(H15), C5(H5), C32(H32), C42(H42), C6(H6), C12(H12), C8(H8),
 C38(H38), C29(H29), C30(H30), C49(H49)
3.c Idealised Me refined as rotating group:
 C109(H10A,H10B,H10C), C108(H10D,H10E,H10F)
;
_shelx_res_checksum              63384
_shelx_hkl_checksum              71005
_shelx_shelxl_version_number     2016/4
_olex2_submission_special_instructions 'No special instructions were received'