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_1517544
_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         'C43 H64 O2 P2 Pd Si'
_chemical_formula_sum            'C43 H64 O2 P2 Pd Si'
_chemical_formula_weight         809.37
_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     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-04-16
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:10:59, GUI svn.r4458)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.432(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.6994(16)
_cell_length_b                   25.260(3)
_cell_length_c                   13.3608(17)
_cell_measurement_reflns_used    17181
_cell_measurement_temperature    93
_cell_measurement_theta_max      24.2
_cell_measurement_theta_min      3.0
_cell_volume                     4131.4(9)
_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
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      93
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
scan:
    Number of images: 180
               Slice: 20.0000 - 200.0000
         Image width: 1.0000
            Exp time: 60.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 45.0000
                 Phi: 270.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 165
               Slice: 20.0000 - 185.0000
         Image width: 1.0000
            Exp time: 60.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 30.0000
                 Phi: 270.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 116
               Slice: 20.0000 - 136.0000
         Image width: 1.0000
            Exp time: 60.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 127.4000
              2theta: 0.0000
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support Unknown
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.010581
_diffrn_orient_matrix_UB_12      -0.039237
_diffrn_orient_matrix_UB_13      -0.004897
_diffrn_orient_matrix_UB_21      -0.043899
_diffrn_orient_matrix_UB_22      0.001782
_diffrn_orient_matrix_UB_23      0.051927
_diffrn_orient_matrix_UB_31      -0.068074
_diffrn_orient_matrix_UB_32      0.004949
_diffrn_orient_matrix_UB_33      -0.057519
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1550
_diffrn_reflns_av_unetI/netI     0.0745
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            59463
_diffrn_reflns_theta_full        24.11
_diffrn_reflns_theta_max         24.11
_diffrn_reflns_theta_min         3.05
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.515
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R (1998) Private Communication'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.692
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     472
_refine_ls_number_reflns         6568
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0597
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0316P)^2^+6.1079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1191
_reflns_number_gt                5442
_reflns_number_total             6568
_reflns_threshold_expression     >2sigma(I)
_cod_duplicate_entry             1516329
_cod_data_source_file            c4sc01110d2.cif
_cod_data_source_block           s12071
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/usr/data/users/saulius/crontab/automatic-downloads/current/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_cell_volume        4131.5(9)
_cod_database_code               1517544
_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. Restrained distances
 C4-C2 \\sim C2-C3A
 with sigma of 0.02
 C3A-C2 \\sim C2-C3
 with sigma of 0.02
 C3-C2 \\sim C2-C4A
 with sigma of 0.02
 C5A-C2 \\sim C2-C5
 with sigma of 0.02
 C6A-C5A \\sim C5-C6
 with sigma of 0.02
3. Rigid bond restraints
 C6A, C5A, C4, C2, C3A, C3, C4A, C6, C5, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C6A \\sim C5A \\sim C4 \\sim C3A \\sim C2 \\sim C3 \\sim C4A \\sim C5 \\sim C6 \\sim C1: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C3A) = Uanis(C2) = Uanis(C5A)
5. Others
 1*Sof(C6A)=1*Sof(H6AC)=1*Sof(H6AD)=1-1*Sof(C5)=1-1*Sof(H5A)=1-1*Sof(C3)=1-1*
 Sof(H3AA)=1-1*Sof(H3AB)=1-1*Sof(H3AC)=1-1*Sof(C6)=1-1*Sof(H6AA)=1-1*Sof(H6AB)=
 1-1*Sof(C4)=1-1*Sof(H4AA)=1-1*Sof(H4AB)=1-1*Sof(H4AC)=1*Sof(C3A)=1*Sof(H3AD)=1*
 Sof(H3AE)=1*Sof(H3AF)=1*Sof(C5A)=1*Sof(H5AA)=1*Sof(C4A)=1*Sof(H4AD)=1*
 Sof(H4AE)=1*Sof(H4AF)
6.a Ternary CH refined with riding coordinates:
 C38(H38), C14(H14), C32(H32), C8(H8)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C16(H16A,H16B), C18(H18A,H18B), C36(H36A,H36B), C11(H11A,
 H11B), C42(H42A,H42B), C39(H39A,H39B), C34(H34A,H34B), C13(H13A,H13B),
 C15(H15A,H15B), C43(H43A,H43B), C41(H41A,H41B), C9(H9A,H9B), C33(H33A,H33B),
 C37(H37A,H37B), C35(H35A,H35B), C19(H19A,H19B), C40(H40A,H40B), C17(H17A,H17B),
  C12(H12A,H12B)
6.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C27(H27), C28(H28), C29(H29), C23(H23), C24(H24), C21(H21),
 C22(H22), C5(H5A), C5A(H5AA)
6.d X=CH2 refined with riding coordinates:
 C6A(H6AC,H6AD), C6(H6AA,H6AB)
6.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C3(H3AA,H3AB,H3AC), C4(H4AA,H4AB,H4AC), C3A(H3AD,H3AE,H3AF),
 C4A(H4AD,H4AE,H4AF)
;