Transient Palladadiphosphanylcarbenes: Singlet Carbenes with an "Inverse" Electronic Configuration (pπ2 instead of σ2) and Unusual Transannular Metal-Carbene Interactions (πC\ρightarrowPd Donation and σPd\ρightarrowC Back-donation)
Joan Vignolle; Heinz Gornitzka; Laurent Maron; Wolfgang W. Schoeller; Didier Bourissou; Guy Bertrand; Journal of the American Chemical Society 129 (2007) 978–985; doi:10.1021/ja066738j

data_4109021
_publ_section_title
;
 Transient Palladadiphosphanylcarbenes: Singlet Carbenes with an "Inverse"
 Electronic Configuration (p\p2 instead of \s2) and Unusual Transannular
 Metal-Carbene Interactions (\pC\\rightarrowPd Donation and
 \sPd\\rightarrowC Back-donation)
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              978
_journal_page_last               985
_journal_paper_doi               10.1021/ja066738j
_journal_volume                  129
_journal_year                    2007
_chemical_formula_sum            'C34 H63 Cl N2 P2 Pd'
_chemical_formula_weight         703.65
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                91.410(2)
_cell_angle_beta                 99.142(2)
_cell_angle_gamma                101.852(2)
_cell_formula_units_Z            2
_cell_length_a                   10.3644(12)
_cell_length_b                   12.5600(15)
_cell_length_c                   14.1755(17)
_cell_measurement_reflns_used    7952
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      26.416
_cell_measurement_theta_min      2.338
_cell_volume                     1779.9(4)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      193(2)
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker CCD detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_sigmaI/netI    0.0444
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15032
_diffrn_reflns_theta_full        26.44
_diffrn_reflns_theta_max         26.44
_diffrn_reflns_theta_min         1.46
_exptl_absorpt_coefficient_mu    0.711
_exptl_absorpt_correction_T_max  1.000000
_exptl_absorpt_correction_T_min  0.872334
_exptl_absorpt_correction_type   semi-empirical
_exptl_absorpt_process_details   'SADABS (Bruker-AXS)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       block
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.898
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         7235
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0333
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0457P)^2^+0.6036P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0815
_refine_ls_wR_factor_ref         0.0891
_reflns_number_gt                5826
_reflns_number_total             7235
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja066738jsi20061108_072313.cif
_cod_data_source_block           3b
_cod_database_code               4109021