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_4109023
_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            'C61 H92 B N2 P3 Pd'
_chemical_formula_weight         1063.49
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_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_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 110.272(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.119(4)
_cell_length_b                   16.313(4)
_cell_length_c                   21.541(5)
_cell_measurement_reflns_used    5351
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      26.470
_cell_measurement_theta_min      2.497
_cell_volume                     5643(2)
_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 0.985
_diffrn_measured_fraction_theta_max 0.985
_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  0.0547
_diffrn_reflns_av_sigmaI/netI    0.0686
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            32210
_diffrn_reflns_theta_full        26.58
_diffrn_reflns_theta_max         26.58
_diffrn_reflns_theta_min         1.60
_exptl_absorpt_coefficient_mu    0.453
_exptl_absorpt_correction_T_max  1.000000
_exptl_absorpt_correction_T_min  0.585079
_exptl_absorpt_correction_type   semi-empirical
_exptl_absorpt_process_details   'SADABS (Bruker-AXS)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       plate
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.655
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     682
_refine_ls_number_reflns         11621
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0439P)^2^+2.4334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0912
_refine_ls_wR_factor_ref         0.1075
_reflns_number_gt                7793
_reflns_number_total             11621
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja066738jsi20061108_072337.cif
_cod_data_source_block           8b
_cod_database_code               4109023