Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Christoph Janiak' 'Paul-Gerhard Lassahn' 'Vasile Lozan' _publ_contact_author_name 'Prof Christoph Janiak' _publ_contact_author_address ; Institut fur Anorganische und Analytische Chemie Universität Freiburg Albertstr. 21 79104 Freiburg 79104 GERMANY ; _publ_contact_author_email JANIAK@UNI-FREIBURG.DE _publ_section_title ; Palladium(II) salts containing [PdCl4]2- and [Pd2Cl6]2- ions as pre-catalysts for the vinyl-polymerization of norbornene - evidence for the in-situ formation of PdCl2 as the active species ; data_plam _database_code_CSD 194665 _audit_creation_method SHELXL-97 _chemical_name_systematic ; acetonyltriphenylphosphonium-hexachlorodipalladate(II) ; _chemical_name_common acetonyltriphenylphosphonium-hexachlorodipalladate(ii) _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C42 H40 Cl6 O2 P2 Pd2' _chemical_formula_weight 1064.22 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.7372(11) _cell_length_b 21.764(2) _cell_length_c 11.8070(10) _cell_angle_alpha 90.00 _cell_angle_beta 119.088(7) _cell_angle_gamma 90.00 _cell_volume 2186.6(4) _cell_formula_units_Z 2 _cell_measurement_temperature 203(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needles _exptl_crystal_colour orangebrown _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.616 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1064 _exptl_absorpt_coefficient_mu 1.297 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _exptl_absorpt_correction_T_min 0.6417 _exptl_absorpt_correction_T_max 0.9380 _exptl_special_details ; An empirical absorption correction on the basis of symmetry-equivalent reflections has been performed with the program SADABS. ; _diffrn_ambient_temperature 203(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker AXS CCD' _diffrn_measurement_method \f-\w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13845 _diffrn_reflns_av_R_equivalents 0.0719 _diffrn_reflns_av_sigmaI/netI 0.1057 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -29 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.18 _diffrn_reflns_theta_max 28.33 _reflns_number_total 5333 _reflns_number_gt 2732 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker 1997a)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker 1997b)' _computing_structure_solution 'SHELXS97, SHELXTL-Plus (Sheldrick, 1997; Sheldrick, 1998)' _computing_structure_refinement 'SHELXL97, SHELXTL-Plus (Sheldrick, 1997; Sheldrick, 1998)' _computing_molecular_graphics 'ORTEP-3 for Windows (Farrugia, 1997)' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The hydrogen atoms on carbon were placed at calculated positions using appropriate riding models (HFIX 43 for aromatic C-H, HFIX 33 for CH3, and HFIX 23 for CH2) and isotropic temperature factors of U(H) = 1.2 Ueq(Carom and CH2) or U(H) = 1.5 Ueq(CH3). ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0285P)^2^+4.4770P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment calc _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5333 _refine_ls_number_parameters 244 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1300 _refine_ls_R_factor_gt 0.0566 _refine_ls_wR_factor_ref 0.1202 _refine_ls_wR_factor_gt 0.0959 _refine_ls_goodness_of_fit_ref 1.021 _refine_ls_restrained_S_all 1.021 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Pd1 Pd 0.53116(6) 0.06014(2) 0.10008(5) 0.03092(14) Uani 1 1 d . . . Cl1 Cl 0.5591(2) 0.16339(7) 0.08634(16) 0.0417(4) Uani 1 1 d . . . Cl2 Cl 0.5533(2) 0.06835(7) 0.29991(15) 0.0417(4) Uani 1 1 d . . . Cl3 Cl 0.5016(2) -0.04577(6) 0.10641(15) 0.0388(4) Uani 1 1 d . . . P1 P 0.09530(18) 0.17064(7) 0.16470(15) 0.0292(4) Uani 1 1 d . . . O1 O 0.2015(5) 0.2582(2) 0.0257(4) 0.0469(12) Uani 1 1 d . . . C1 C 0.2878(7) 0.2051(3) 0.2249(6) 0.0353(15) Uani 1 1 d . . . H1A H 0.3213 0.2218 0.3116 0.042 Uiso 1 1 calc R . . H1B H 0.3627 0.1729 0.2337 0.042 Uiso 1 1 calc R . . C2 C 0.2954(7) 0.2564(3) 0.1395(6) 0.0339(15) Uani 1 1 d . . . C3 C 0.4251(9) 0.3023(3) 0.2047(7) 0.055(2) Uani 1 1 d . . . H3A H 0.4176 0.3328 0.1422 0.082 Uiso 1 1 calc R . . H3B H 0.5257 0.2815 0.2401 0.082 Uiso 1 1 calc R . . H3C H 0.4160 0.3222 0.2742 0.082 Uiso 1 1 calc R . . C11 C 0.1074(7) 0.1269(2) 0.2989(6) 0.0306(14) Uani 1 1 d . . . C12 C -0.0206(8) 0.1211(3) 0.3195(6) 0.0381(16) Uani 1 1 d . . . H12 H -0.1166 0.1400 0.2625 0.046 Uiso 1 1 calc R . . C13 C -0.0068(9) 0.0878(3) 0.4233(7) 0.0500(19) Uani 1 1 d . . . H13 H -0.0930 0.0843 0.4380 0.060 Uiso 1 1 calc R . . C14 C 0.1329(8) 0.0598(3) 0.5055(6) 0.0421(16) Uani 1 1 d . . . H14 H 0.1420 0.0378 0.5773 0.051 Uiso 1 1 calc R . . C15 C 0.2601(8) 0.0634(3) 0.4846(6) 0.0428(16) Uani 1 1 d . . . H15 H 0.3549 0.0435 0.5406 0.051 Uiso 1 1 calc R . . C16 C 0.2460(8) 0.0968(3) 0.3799(6) 0.0385(16) Uani 1 1 d . . . H16 H 0.3314 0.0992 0.3638 0.046 Uiso 1 1 calc R . . C21 C 0.0436(7) 0.1211(2) 0.0287(6) 0.0273(13) Uani 1 1 d . . . C22 C -0.0965(8) 0.0888(3) -0.0227(6) 0.0351(15) Uani 1 1 d . . . H22 H -0.1641 0.0947 0.0123 0.042 Uiso 1 1 calc R . . C23 C -0.1387(8) 0.0484(3) -0.1237(6) 0.0394(16) Uani 1 1 d . . . H23 H -0.2345 0.0271 -0.1580 0.047 Uiso 1 1 calc R . . C24 C -0.0390(8) 0.0397(3) -0.1742(6) 0.0401(16) Uani 1 1 d . . . H24 H -0.0672 0.0124 -0.2438 0.048 Uiso 1 1 calc R . . C25 C 0.1017(8) 0.0706(3) -0.1230(6) 0.0414(16) Uani 1 1 d . . . H25 H 0.1697 0.0638 -0.1572 0.050 Uiso 1 1 calc R . . C26 C 0.1446(8) 0.1117(3) -0.0222(6) 0.0375(16) Uani 1 1 d . . . H26 H 0.2404 0.1331 0.0116 0.045 Uiso 1 1 calc R . . C31 C -0.0479(7) 0.2298(2) 0.1220(5) 0.0266(13) Uani 1 1 d . . . C32 C -0.1469(7) 0.2442(3) -0.0066(6) 0.0306(14) Uani 1 1 d . . . H32 H -0.1445 0.2206 -0.0724 0.037 Uiso 1 1 calc R . . C33 C -0.2499(7) 0.2935(3) -0.0388(6) 0.0361(15) Uani 1 1 d . . . H33 H -0.3152 0.3039 -0.1262 0.043 Uiso 1 1 calc R . . C34 C -0.2561(7) 0.3269(3) 0.0570(6) 0.0363(15) Uani 1 1 d . . . H34 H -0.3278 0.3595 0.0352 0.044 Uiso 1 1 calc R . . C35 C -0.1577(8) 0.3128(3) 0.1845(6) 0.0400(16) Uani 1 1 d . . . H35 H -0.1618 0.3363 0.2496 0.048 Uiso 1 1 calc R . . C36 C -0.0526(8) 0.2644(3) 0.2190(6) 0.0370(16) Uani 1 1 d . . . H36 H 0.0147 0.2552 0.3068 0.044 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Pd1 0.0295(3) 0.0291(2) 0.0324(3) -0.0025(2) 0.0137(2) -0.0007(2) Cl1 0.0459(10) 0.0277(8) 0.0451(10) -0.0034(7) 0.0172(9) -0.0046(7) Cl2 0.0509(10) 0.0408(9) 0.0329(9) -0.0034(7) 0.0201(8) 0.0024(8) Cl3 0.0528(11) 0.0308(9) 0.0395(9) -0.0015(7) 0.0277(9) -0.0032(7) P1 0.0280(8) 0.0262(8) 0.0249(9) 0.0016(7) 0.0063(8) 0.0013(7) O1 0.044(3) 0.049(3) 0.027(3) 0.009(2) 0.001(2) -0.006(2) C1 0.032(4) 0.032(3) 0.031(4) 0.002(3) 0.006(3) 0.000(3) C2 0.030(4) 0.030(3) 0.038(4) 0.001(3) 0.013(3) 0.002(3) C3 0.063(5) 0.033(4) 0.045(5) 0.005(3) 0.008(4) -0.019(4) C11 0.039(4) 0.021(3) 0.030(4) -0.001(2) 0.015(3) -0.001(3) C12 0.035(4) 0.033(4) 0.046(4) 0.008(3) 0.019(4) 0.005(3) C13 0.054(5) 0.041(4) 0.065(5) 0.009(4) 0.036(5) -0.001(4) C14 0.055(4) 0.031(3) 0.036(4) 0.006(3) 0.018(4) -0.005(3) C15 0.044(4) 0.028(3) 0.042(4) 0.016(3) 0.009(3) 0.007(3) C16 0.034(4) 0.038(4) 0.039(4) 0.007(3) 0.014(3) 0.006(3) C21 0.029(3) 0.023(3) 0.025(3) 0.005(2) 0.010(3) 0.005(2) C22 0.037(4) 0.030(3) 0.037(4) 0.004(3) 0.017(3) -0.002(3) C23 0.039(4) 0.036(4) 0.036(4) 0.000(3) 0.012(3) -0.006(3) C24 0.050(4) 0.033(4) 0.025(4) -0.005(3) 0.008(3) -0.006(3) C25 0.040(4) 0.042(4) 0.041(4) -0.001(3) 0.019(3) 0.009(3) C26 0.033(4) 0.036(4) 0.037(4) -0.003(3) 0.013(3) 0.000(3) C31 0.029(3) 0.025(3) 0.021(3) 0.002(2) 0.009(3) -0.003(2) C32 0.032(3) 0.032(3) 0.022(3) -0.002(3) 0.009(3) 0.004(3) C33 0.037(4) 0.036(4) 0.024(3) 0.008(3) 0.006(3) 0.004(3) C34 0.036(4) 0.036(4) 0.038(4) 0.004(3) 0.018(3) 0.005(3) C35 0.052(4) 0.032(4) 0.034(4) -0.003(3) 0.020(4) 0.004(3) C36 0.051(4) 0.033(3) 0.020(3) 0.008(3) 0.011(3) 0.007(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Pd1 Cl2 2.2695(16) . ? Pd1 Cl1 2.2787(16) . ? Pd1 Cl3 2.3212(16) 3_655 ? Pd1 Cl3 2.3286(15) . ? Pd1 Pd1 3.3781(9) 3_655 ? Cl3 Pd1 2.3212(16) 3_655 ? P1 C31 1.781(6) . ? P1 C21 1.792(6) . ? P1 C11 1.803(6) . ? P1 C1 1.813(6) . ? O1 C2 1.203(7) . ? C1 C2 1.530(8) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C2 C3 1.497(8) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C3 H3C 0.9700 . ? C11 C16 1.382(8) . ? C11 C12 1.386(8) . ? C12 C13 1.373(9) . ? C12 H12 0.9400 . ? C13 C14 1.371(9) . ? C13 H13 0.9400 . ? C14 C15 1.378(9) . ? C14 H14 0.9400 . ? C15 C16 1.383(8) . ? C15 H15 0.9400 . ? C16 H16 0.9400 . ? C21 C22 1.384(8) . ? C21 C26 1.394(8) . ? C22 C23 1.374(8) . ? C22 H22 0.9400 . ? C23 C24 1.377(9) . ? C23 H23 0.9400 . ? C24 C25 1.376(9) . ? C24 H24 0.9400 . ? C25 C26 1.381(8) . ? C25 H25 0.9400 . ? C26 H26 0.9400 . ? C31 C32 1.382(7) . ? C31 C36 1.391(8) . ? C32 C33 1.390(8) . ? C32 H32 0.9400 . ? C33 C34 1.371(8) . ? C33 H33 0.9400 . ? C34 C35 1.370(8) . ? C34 H34 0.9400 . ? C35 C36 1.384(8) . ? C35 H35 0.9400 . ? C36 H36 0.9400 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl2 Pd1 Cl1 92.41(6) . . ? Cl2 Pd1 Cl3 176.11(6) . 3_655 ? Cl1 Pd1 Cl3 91.05(6) . 3_655 ? Cl2 Pd1 Cl3 89.73(6) . . ? Cl1 Pd1 Cl3 177.86(6) . . ? Cl3 Pd1 Cl3 86.81(5) 3_655 . ? Cl2 Pd1 Pd1 133.02(5) . 3_655 ? Cl1 Pd1 Pd1 134.54(5) . 3_655 ? Cl3 Pd1 Pd1 43.49(4) 3_655 3_655 ? Cl3 Pd1 Pd1 43.32(4) . 3_655 ? Pd1 Cl3 Pd1 93.19(5) 3_655 . ? C31 P1 C21 110.0(3) . . ? C31 P1 C11 109.8(3) . . ? C21 P1 C11 109.8(3) . . ? C31 P1 C1 109.3(3) . . ? C21 P1 C1 112.8(3) . . ? C11 P1 C1 105.1(3) . . ? C2 C1 P1 114.6(4) . . ? C2 C1 H1A 108.6 . . ? P1 C1 H1A 108.6 . . ? C2 C1 H1B 108.6 . . ? P1 C1 H1B 108.6 . . ? H1A C1 H1B 107.6 . . ? O1 C2 C3 123.0(6) . . ? O1 C2 C1 120.5(5) . . ? C3 C2 C1 116.5(5) . . ? C2 C3 H3A 109.5 . . ? C2 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C2 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? C16 C11 C12 119.7(6) . . ? C16 C11 P1 118.9(5) . . ? C12 C11 P1 121.4(5) . . ? C13 C12 C11 119.8(6) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C14 C13 C12 120.0(7) . . ? C14 C13 H13 120.0 . . ? C12 C13 H13 120.0 . . ? C13 C14 C15 121.1(6) . . ? C13 C14 H14 119.5 . . ? C15 C14 H14 119.5 . . ? C14 C15 C16 118.9(6) . . ? C14 C15 H15 120.6 . . ? C16 C15 H15 120.6 . . ? C11 C16 C15 120.4(6) . . ? C11 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? C22 C21 C26 119.3(6) . . ? C22 C21 P1 119.0(5) . . ? C26 C21 P1 121.6(5) . . ? C23 C22 C21 121.3(6) . . ? C23 C22 H22 119.4 . . ? C21 C22 H22 119.4 . . ? C22 C23 C24 119.2(6) . . ? C22 C23 H23 120.4 . . ? C24 C23 H23 120.4 . . ? C25 C24 C23 120.2(6) . . ? C25 C24 H24 119.9 . . ? C23 C24 H24 119.9 . . ? C24 C25 C26 121.0(6) . . ? C24 C25 H25 119.5 . . ? C26 C25 H25 119.5 . . ? C25 C26 C21 119.0(6) . . ? C25 C26 H26 120.5 . . ? C21 C26 H26 120.5 . . ? C32 C31 C36 119.9(5) . . ? C32 C31 P1 120.4(4) . . ? C36 C31 P1 119.6(4) . . ? C31 C32 C33 120.0(5) . . ? C31 C32 H32 120.0 . . ? C33 C32 H32 120.0 . . ? C34 C33 C32 120.0(6) . . ? C34 C33 H33 120.0 . . ? C32 C33 H33 120.0 . . ? C35 C34 C33 120.0(6) . . ? C35 C34 H34 120.0 . . ? C33 C34 H34 120.0 . . ? C34 C35 C36 121.1(6) . . ? C34 C35 H35 119.5 . . ? C36 C35 H35 119.5 . . ? C35 C36 C31 119.0(6) . . ? C35 C36 H36 120.5 . . ? C31 C36 H36 120.5 . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 28.33 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 1.056 _refine_diff_density_min -1.286 _refine_diff_density_rms 0.163