gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation
Tay, Dillon W. P.; Nobbs, James D.; Romain, Charles; White, Andrew J. P.; Aitipamula, Srinivasulu; van Meurs, Martin; Britovsek, George J. P.; ACS Catalysis 10 (2019) 663–; doi:10.1021/acscatal.9b03007

data_4517216
_publ_section_title
;
 gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination
 Behavior, and Application in Pd-Catalyzed Hydroformylation
;
_journal_issue                   1
_journal_name_full               'ACS Catalysis'
_journal_page_first              663
_journal_paper_doi               10.1021/acscatal.9b03007
_journal_volume                  10
_journal_year                    2019
_chemical_formula_moiety         'C33 H38 Cl2 P2 Pd'
_chemical_formula_sum            'C33 H38 Cl2 P2 Pd'
_chemical_formula_weight         673.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.081(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2984(5)
_cell_length_b                   20.6157(8)
_cell_length_c                   14.1400(6)
_cell_measurement_reflns_used    6759
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.2260
_cell_measurement_theta_min      3.3360
_cell_volume                     3093.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2945
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.863
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     -5.00 103.00   1.00   58.98    --   18.83  57.00  60.00  108
  2  \w     35.00 106.00   1.00   58.98    --   18.83-178.00  30.00   71
  3  \w    -13.00  22.00   1.00   58.98    --  -19.45 -99.00  60.00   35
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0066991000
_diffrn_orient_matrix_UB_12      0.0342314000
_diffrn_orient_matrix_UB_13      -0.0029619000
_diffrn_orient_matrix_UB_21      -0.0215737000
_diffrn_orient_matrix_UB_22      -0.0003999000
_diffrn_orient_matrix_UB_23      0.0415507000
_diffrn_orient_matrix_UB_31      0.0628920000
_diffrn_orient_matrix_UB_32      0.0035158000
_diffrn_orient_matrix_UB_33      0.0334329000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14685
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.090
_diffrn_reflns_theta_min         2.755
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.897
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.562
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            colorless
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_description       needle
_exptl_crystal_F_000             1384
_exptl_crystal_preparation       'Vapor diffusion'
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.472
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.061
_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     347
_refine_ls_number_reflns         7841
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0352
_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^)+(0.0324P)^2^+0.3796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0829
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5960
_reflns_number_total             7841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03007_si_002.cif
_cod_data_source_block           Pd-L4-Cl2
_cod_depositor_comments
'Adding full bibliography for 4517213--4517216.cif.'
_cod_database_code               4517216
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C20 H24 P2 Pd1 Cl2'
_reflns_odcompleteness_completeness 99.36
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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 Ternary CH refined with riding coordinates:
 C7(H7), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C15(H15), C14(H14), C11(H11), C17(H17), C23(H23), C33(H33),
 C13(H13), C29(H29), C24(H24), C26(H26), C21(H21), C12(H12), C32(H32), C31(H31),
  C18(H18), C19(H19), C25(H25), C30(H30), C20(H20)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              48400
_shelx_hkl_checksum              71735
_olex2_date_sample_data_collection 2019-04-16
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.531
_oxdiff_exptl_absorpt_empirical_full_min 0.811