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_1517542
_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         837.51
_chemical_name_systematic
;
 ? 
;
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 102.802(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.1665(11)
_cell_length_b                   10.3002(7)
_cell_length_c                   27.3994(19)
_cell_measurement_reflns_used    21810
_cell_measurement_temperature    150
_cell_measurement_theta_max      23.8
_cell_measurement_theta_min      3.0
_cell_volume                     4449.1(5)
_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      150
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 120.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 180.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 0.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 240.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 90.0000
                 XTD: 127.4000
              2theta: -0.0057
scan:
    Number of images: 90
               Slice: 20.0000 - 200.0000
         Image width: 2.0000
            Exp time: 70.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 180.0000
                 XTD: 127.4000
              2theta: -0.0057
;
_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      0.010187
_diffrn_orient_matrix_UB_12      -0.083158
_diffrn_orient_matrix_UB_13      -0.016569
_diffrn_orient_matrix_UB_21      0.057330
_diffrn_orient_matrix_UB_22      -0.007000
_diffrn_orient_matrix_UB_23      0.022892
_diffrn_orient_matrix_UB_31      -0.025164
_diffrn_orient_matrix_UB_32      -0.049613
_diffrn_orient_matrix_UB_33      0.024541
_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  0.1570
_diffrn_reflns_av_unetI/netI     0.1017
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            37324
_diffrn_reflns_theta_full        23.82
_diffrn_reflns_theta_max         23.82
_diffrn_reflns_theta_min         3.02
_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    0.546
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.228
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R (1998) Private Communication'
_exptl_crystal_colour            Colorless
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.645
_refine_diff_density_min         -1.200
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     495
_refine_ls_number_reflns         6808
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1038
_refine_ls_R_factor_gt           0.0628
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0611P)^2^+1.3362P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1269
_refine_ls_wR_factor_ref         0.1453
_reflns_number_gt                4558
_reflns_number_total             6808
_reflns_threshold_expression     >2sigma(I)
_cod_duplicate_entry             1516327
_cod_data_source_file            c4sc01110d2.cif
_cod_data_source_block           s12103
_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_database_code               1517542
_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
 C44-C45 \\sim C45-C46
 with sigma of 0.02
 C45-C46 \\sim C46-C47
 with sigma of 0.02
 C45-C44 \\sim C44-C43
 with sigma of 0.02
 C43A-C44A \\sim C44A-C45A
 with sigma of 0.02
 C44A-C45A \\sim C45A-C46A
 with sigma of 0.02
 C45A-C46A \\sim C46A-C47A
 with sigma of 0.02
3. Rigid bond restraints
 C43, C44, C45, C46, C47
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43A, C44A, C45A, C46A, C47A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43, C46, C44, C47, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C47A \\sim C46A \\sim C45A \\sim C44A \\sim C43A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C43 \\sim C46 \\sim C44 \\sim C47 \\sim C45: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C43A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C43A) = Uanis(C44A) = Uanis(C45A)
Uanis(C47) = Uanis(C46)
5. Others
 1-1*Sof(C43)=1-1*Sof(H43D)=1-1*Sof(H43E)=1-1*Sof(H43F)=1-1*Sof(C46)=1-1*
 Sof(H46C)=1-1*Sof(H46D)=1-1*Sof(C44)=1-1*Sof(H44C)=1-1*Sof(H44D)=1-1*Sof(C47)=
 1-1*Sof(H47D)=1-1*Sof(H47E)=1-1*Sof(H47F)=1-1*Sof(C45)=1-1*Sof(H45C)=1-1*
 Sof(H45D)=1*Sof(C44A)=1*Sof(H44A)=1*Sof(H44B)=1*Sof(C47A)=1*Sof(H47A)=1*
 Sof(H47B)=1*Sof(H47C)=1*Sof(C46A)=1*Sof(H46A)=1*Sof(H46B)=1*Sof(C43A)=1*
 Sof(H43A)=1*Sof(H43B)=1*Sof(H43C)=1*Sof(C45A)=1*Sof(H45A)=1*Sof(H45B)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C6(H6), C37(H37), C31(H31)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C17(H17A,H17B), C11(H11A,H11B), C14(H14A,H14B),
 C38(H38A,H38B), C13(H13A,H13B), C32(H32A,H32B), C39(H39A,H39B), C42(H42A,H42B),
  C9(H9A,H9B), C10(H10A,H10B), C8(H8A,H8B), C41(H41A,H41B), C34(H34A,H34B),
 C36(H36A,H36B), C33(H33A,H33B), C35(H35A,H35B), C15(H15A,H15B), C16(H16A,H16B),
  C40(H40A,H40B), C46(H46C,H46D), C44(H44C,H44D), C45(H45C,H45D), C44A(H44A,
 H44B), C46A(H46A,H46B), C45A(H45A,H45B)
6.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C19(H19), C29(H29), C28(H28), C26(H26), C22(H22), C27(H27), C2(H2),
 C20(H20)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C43(H43D,H43E,H43F),
 C47(H47D,H47E,H47F), C47A(H47A,H47B,H47C), C43A(H43A,H43B,H43C)
;