A mechanistic study of allene carboxylation with CO2resulting in the development of a Pd(ii) pincer complex for the catalytic hydroboration of CO2
Suh, Hee-Won; Guard, Louise M.; Hazari, Nilay; Chemical Science 5 (2014) 3859–; doi:10.1039/C4SC01110D

data_1517543
_publ_section_title
;
 A mechanistic study of allene carboxylation with CO2resulting in the
 development of a Pd(ii) pincer complex for the catalytic hydroboration of
 CO2
;
_journal_issue                   10
_journal_name_full               'Chemical Science'
_journal_page_first              3859
_journal_paper_doi               10.1039/C4SC01110D
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C42 H64 P2 Pd Si, C5 H12'
_chemical_formula_sum            'C47 H76 P2 Pd Si'
_chemical_formula_weight         837.50
_chemical_name_systematic
;
 ? 
;
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-24
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 106.453(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.8954(3)
_cell_length_b                   18.9114(3)
_cell_length_c                   16.6032(12)
_cell_measurement_reflns_used    46969
_cell_measurement_temperature    93
_cell_measurement_theta_max      63.7
_cell_measurement_theta_min      2.3
_cell_volume                     4485.5(4)
_computing_cell_refinement
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      93
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -48.0000 - 132.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 360
               Slice: -48.0000 - 132.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 15.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 344
               Slice: -48.0000 - 124.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 30.0000
                 Phi: 90.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 348
               Slice: -48.0000 - 126.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 270
               Slice: -14.0000 - 121.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 0.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 360
               Slice: -48.0000 - 132.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 90.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 240
               Slice: -18.0000 - 102.0000
         Image width: 0.5000
            Exp time: 1.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 42.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 15.0000
                 Phi: 90.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 15.0000
                 Phi: 0.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 15.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 0.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 30.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 30.0000
                 Phi: 90.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 328
               Slice: 0.0000 - 164.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 180.0000
                 XTD: 50.0000
              2theta: 90.0000
scan:
    Number of images: 360
               Slice: 0.0000 - 180.0000
         Image width: 0.5000
            Exp time: 3.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 90.0000
                 XTD: 50.0000
              2theta: 90.0000
;
_diffrn_measurement_device
;
AFC11 (Left): Eulerian 3 circle
;
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       \w
_diffrn_measurement_specimen_support Unknown
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.030047
_diffrn_orient_matrix_UB_12      0.006508
_diffrn_orient_matrix_UB_13      -0.061526
_diffrn_orient_matrix_UB_21      0.041364
_diffrn_orient_matrix_UB_22      0.041642
_diffrn_orient_matrix_UB_23      -0.000038
_diffrn_orient_matrix_UB_31      0.047816
_diffrn_orient_matrix_UB_32      -0.031933
_diffrn_orient_matrix_UB_33      -0.012590
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_type           CuKa
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            52296
_diffrn_reflns_theta_full        63.69
_diffrn_reflns_theta_max         63.69
_diffrn_reflns_theta_min         3.52
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.477
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private Communication'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.240
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.968
_refine_diff_density_min         -0.990
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     465
_refine_ls_number_reflns         7332
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0418
_refine_ls_R_factor_gt           0.0398
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0690P)^2^+5.4438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1061
_refine_ls_wR_factor_ref         0.1077
_reflns_number_gt                6896
_reflns_number_total             7332
_reflns_threshold_expression     >2sigma(I)
_cod_duplicate_entry             1516328
_cod_data_source_file            c4sc01110d2.cif
_cod_data_source_block           00713008
_cod_depositor_comments
;

2019-03-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         418.75
_cod_original_formula_units_Z            8
_cod_original_cell_volume        4485.5(3)
_cod_original_formula_sum        'C23.50 H38 P Pd0.50 Si0.50'
_cod_database_code               1517543
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H26 of C26, H11 of C11, {H42a,H42b} of C42, {H40a,H40b} of C40, {H2a,H2b}
  of C2, {H39a,H39b} of C39, H10 of C10, {H38a,H38b} of C38, {H32a,H32b} of C32,
   H8 of C8, H29 of C29, H31 of C31, H37 of C37, H27 of C27, H3 of C3, H9 of C9,
   {H18a,H18b} of C18, H28 of C28, {H21a,H21b} of C21, {H22a,H22b} of C22,
  {H16a,H16b} of C16, {H33a,H33b} of C33, {H17a,H17b} of C17, {H35a,H35b} of
  C35, {H34a,H34b} of C34, {H1Ba,H1Bb} of C1B, {H1Da,H1Db} of C1D, H19 of C19,
  {H20a,H20b} of C20, {H14a,H14b} of C14, {H41a,H41b} of C41, {H15a,H15b} of
  C15, {H24a,H24b} of C24, {H36a,H36b} of C36, H13 of C13, {H23a,H23b} of C23,
  {H1Wa,H1Wb} of C1W
 At 1.5 times of:
  {H5a,H5b,H5c} of C5, {H6a,H6b,H6c} of C6, {H1Aa,H1Ab,H1Ac} of C1A, {H1Ca,
  H1Cb,H1Cc} of C1C, {H1a,H1b,H1c} of C1
2. Restrained distances
 C1C-C1D ~ C1D-C1W
 with sigma of 0.02
 C1D-C1W ~ C1W-C1B
 with sigma of 0.02
 C1W-C1B ~ C1B-C1A
 with sigma of 0.02
3. Rigid bond restraints
 C1A, C1B, C1W, C1D, C1C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1A ~ C1B ~ C1W ~ C1D ~ C1C: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
5.a Ternary CH refined with riding coordinates:
 C37(H37), C31(H31), C19(H19), C13(H13)
5.b Secondary CH2 refined with riding coordinates:
 C38(H38a,H38b), C42(H42a,H42b), C2(H2a,H2b), C39(H39a,H39b), C40(H40a,H40b),
 C32(H32a,H32b), C20(H20a,H20b), C14(H14a,H14b), C41(H41a,H41b), C15(H15a,H15b),
  C24(H24a,H24b), C36(H36a,H36b), C23(H23a,H23b), C18(H18a,H18b), C21(H21a,
 H21b), C22(H22a,H22b), C16(H16a,H16b), C33(H33a,H33b), C17(H17a,H17b),
 C35(H35a,H35b), C34(H34a,H34b), C1B(H1Ba,H1Bb), C1D(H1Da,H1Db), C1W(H1Wa,H1Wb)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C26(H26), C10(H10), C8(H8), C27(H27), C29(H29), C3(H3), C9(H9),
 C28(H28)
5.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C1A(H1Aa,H1Ab,H1Ac),
 C1C(H1Ca,H1Cb,H1Cc)
;