# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Luciano Canovese' _publ_contact_author_email CANO@UNIVE.IT _publ_section_title ; Substitution Reactions between Bis-chelate Ligands in Palladium(II) Alkenyl Complexes. An Unusual Way to the Formation of Unstable Trans-P Complexes. A Study on the Isomerization Mechanism. ; loop_ _publ_author_name 'Luciano Canovese' 'Gavino Chessa' 'Alessandro Dolmella' 'Claudio Santo' 'Fabiano Visentin' # Attachment 'LC09CIF.cif' data_lc09 _database_code_depnum_ccdc_archive 'CCDC 735035' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H25 Cl N O4 P Pd' _chemical_formula_weight 612.31 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' N N 0.0061 0.0033 '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' Cl Cl 0.1484 0.1585 '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 'P2(1)/n (No.14)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/ 2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.279(2) _cell_length_b 17.499(4) _cell_length_c 16.897(3) _cell_angle_alpha 90.00 _cell_angle_beta 104.62(3) _cell_angle_gamma 90.00 _cell_volume 2654.8(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 30 _cell_measurement_theta_min 12.00 _cell_measurement_theta_max 15.00 _exptl_crystal_description rhomboids _exptl_crystal_colour yellow _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.532 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1240 _exptl_absorpt_coefficient_mu 0.894 _exptl_absorpt_correction_type psi-scans _exptl_absorpt_correction_T_min 0.662 _exptl_absorpt_correction_T_max 0.857 _exptl_absorpt_process_details '(North et al., 1968)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Philips PW1100 dffractometer' _diffrn_measurement_method 'omega-2 theta' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time ? _diffrn_standards_decay_% negligible _diffrn_reflns_number 5947 _diffrn_reflns_av_R_equivalents 0.0353 _diffrn_reflns_av_sigmaI/netI 0.0340 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.08 _diffrn_reflns_theta_max 27.04 _reflns_number_total 5760 _reflns_number_gt 5102 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'FEBO system' _computing_cell_refinement 'FEBO system' _computing_data_reduction 'FEBO system' _computing_structure_solution 'SHELXTL NT vers.5.10 (Sheldrick, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL NT vers.5.10 (Sheldrick, 1999)' _computing_publication_material 'SHELXTL NT vers.5.10 (Sheldrick, 1999)' _refine_special_details ; Refinement of F^2^ against ALL refle ctions. 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 dat a will be even larger. ; _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^)+(0.0000P)^2^+7.1021P] 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 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5760 _refine_ls_number_parameters 325 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0600 _refine_ls_R_factor_gt 0.0486 _refine_ls_wR_factor_ref 0.1244 _refine_ls_wR_factor_gt 0.1150 _refine_ls_goodness_of_fit_ref 1.317 _refine_ls_restrained_S_all 1.317 _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 Pd Pd 0.80925(4) 0.136069(19) 0.132711(19) 0.03603(11) Uani 1 1 d . . . Cl Cl 0.84124(18) 0.01056(8) 0.09349(10) 0.0672(4) Uani 1 1 d . . . P P 0.77522(12) 0.25597(6) 0.16296(6) 0.0348(2) Uani 1 1 d . . . N N 0.9284(4) 0.1834(2) 0.0515(2) 0.0419(8) Uani 1 1 d . . . O1 O 0.7640(4) 0.1441(2) 0.3429(2) 0.0583(9) Uani 1 1 d . . . O2 O 0.8571(4) 0.0352(2) 0.3097(2) 0.0571(9) Uani 1 1 d . . . O3 O 0.5147(5) 0.0294(3) 0.3052(2) 0.0659(11) Uani 1 1 d . . . O4 O 0.3133(5) 0.0513(3) 0.2050(3) 0.0926(17) Uani 1 1 d . . . C1 C 0.6838(5) 0.1000(3) 0.2061(3) 0.0391(9) Uani 1 1 d . . . C2 C 0.7670(5) 0.0955(3) 0.2933(3) 0.0414(10) Uani 1 1 d . . . C3 C 0.5407(5) 0.0841(3) 0.1796(3) 0.0444(10) Uani 1 1 d . . . C4 C 0.4521(6) 0.0965(4) 0.0926(3) 0.0622(15) Uani 1 1 d . . . H4A H 0.5159 0.1169 0.0611 0.093 Uiso 1 1 calc R . . H4B H 0.3726 0.1318 0.0919 0.093 Uiso 1 1 calc R . . H4C H 0.4113 0.0487 0.0695 0.093 Uiso 1 1 calc R . . C5 C 0.4589(6) 0.0523(3) 0.2376(3) 0.0518(12) Uani 1 1 d . . . C6 C 1.0024(6) 0.1433(3) 0.0092(3) 0.0537(12) Uani 1 1 d . . . H6A H 1.0121 0.0910 0.0183 0.064 Uiso 1 1 calc R . . C7 C 1.0674(7) 0.1760(4) -0.0493(4) 0.0686(17) Uani 1 1 d . . . H7A H 1.1185 0.1454 -0.0781 0.082 Uiso 1 1 calc R . . C8 C 1.0557(6) 0.2515(3) -0.0636(3) 0.0587(14) Uani 1 1 d . . . H8A H 1.0995 0.2734 -0.1020 0.070 Uiso 1 1 calc R . . C9 C 0.9775(5) 0.2972(3) -0.0206(3) 0.0485(12) Uani 1 1 d . . . C10 C 0.9589(6) 0.3763(3) -0.0322(3) 0.0573(13) Uani 1 1 d . . . H10A H 0.9947 0.4003 -0.0725 0.069 Uiso 1 1 calc R . . C11 C 0.8895(6) 0.4178(3) 0.0143(4) 0.0588(13) Uani 1 1 d . . . H11A H 0.8786 0.4702 0.0057 0.071 Uiso 1 1 calc R . . C12 C 0.8338(6) 0.3839(3) 0.0752(3) 0.0514(12) Uani 1 1 d . . . H12A H 0.7903 0.4137 0.1085 0.062 Uiso 1 1 calc R . . C13 C 0.8439(5) 0.3059(3) 0.0856(3) 0.0389(9) Uani 1 1 d . . . C14 C 0.9162(5) 0.2614(3) 0.0387(2) 0.0389(9) Uani 1 1 d . . . C15 C 0.8871(5) 0.2923(3) 0.2589(2) 0.0385(9) Uani 1 1 d . . . C16 C 0.8533(6) 0.3587(3) 0.2950(3) 0.0512(12) Uani 1 1 d . . . H16A H 0.7659 0.3850 0.2716 0.061 Uiso 1 1 calc R . . C17 C 0.9493(7) 0.3859(4) 0.3657(3) 0.0623(14) Uani 1 1 d . . . H17A H 0.9257 0.4299 0.3905 0.075 Uiso 1 1 calc R . . C18 C 1.0788(7) 0.3480(4) 0.3989(3) 0.0724(18) Uani 1 1 d . . . H18A H 1.1443 0.3668 0.4459 0.087 Uiso 1 1 calc R . . C19 C 1.1130(7) 0.2823(4) 0.3634(3) 0.077(2) Uani 1 1 d . . . H19A H 1.2015 0.2569 0.3867 0.092 Uiso 1 1 calc R . . C20 C 1.0181(6) 0.2536(3) 0.2939(3) 0.0561(13) Uani 1 1 d . . . H20A H 1.0414 0.2087 0.2705 0.067 Uiso 1 1 calc R . . C21 C 0.5873(5) 0.2881(3) 0.1516(3) 0.0394(9) Uani 1 1 d . . . C22 C 0.5004(5) 0.3132(3) 0.0767(3) 0.0474(11) Uani 1 1 d . . . H22A H 0.5408 0.3162 0.0317 0.057 Uiso 1 1 calc R . . C23 C 0.3543(6) 0.3336(3) 0.0693(4) 0.0596(14) Uani 1 1 d . . . H23A H 0.2961 0.3499 0.0189 0.072 Uiso 1 1 calc R . . C24 C 0.2939(6) 0.3302(4) 0.1347(4) 0.0688(16) Uani 1 1 d . . . H24A H 0.1959 0.3454 0.1295 0.083 Uiso 1 1 calc R . . C25 C 0.3781(7) 0.3044(5) 0.2080(4) 0.0766(19) Uani 1 1 d . . . H25A H 0.3361 0.3008 0.2523 0.092 Uiso 1 1 calc R . . C26 C 0.5238(6) 0.2836(4) 0.2170(3) 0.0579(14) Uani 1 1 d . . . H26A H 0.5801 0.2665 0.2675 0.069 Uiso 1 1 calc R . . C27 C 0.9551(7) 0.0324(4) 0.3903(4) 0.0769(19) Uani 1 1 d . . . H27A H 1.0150 -0.0130 0.3958 0.115 Uiso 1 1 calc R . . H27B H 0.8974 0.0317 0.4301 0.115 Uiso 1 1 calc R . . H27C H 1.0186 0.0765 0.3989 0.115 Uiso 1 1 calc R . . C28 C 0.2243(10) 0.0190(8) 0.2548(6) 0.154(5) Uani 1 1 d . . . H28A H 0.1211 0.0210 0.2257 0.232 Uiso 1 1 calc R . . H28B H 0.2391 0.0476 0.3047 0.232 Uiso 1 1 calc R . . H28C H 0.2531 -0.0332 0.2672 0.232 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 Pd 0.03880(18) 0.04060(19) 0.03080(17) -0.00259(13) 0.01269(12) -0.00260(13) Cl 0.0852(10) 0.0466(7) 0.0836(10) -0.0176(7) 0.0471(8) -0.0092(7) P 0.0343(5) 0.0407(6) 0.0301(5) 0.0006(4) 0.0094(4) 0.0006(4) N 0.045(2) 0.048(2) 0.0352(18) -0.0064(16) 0.0159(16) -0.0073(17) O1 0.072(2) 0.060(2) 0.0411(18) -0.0111(16) 0.0120(17) 0.0066(18) O2 0.062(2) 0.062(2) 0.0431(18) 0.0019(16) 0.0055(16) 0.0164(18) O3 0.069(2) 0.087(3) 0.047(2) 0.0126(19) 0.0235(18) -0.010(2) O4 0.046(2) 0.151(5) 0.079(3) 0.033(3) 0.014(2) -0.029(3) C1 0.047(2) 0.040(2) 0.033(2) 0.0023(17) 0.0146(18) 0.0002(19) C2 0.043(2) 0.047(2) 0.036(2) 0.0028(19) 0.0153(18) 0.000(2) C3 0.048(3) 0.053(3) 0.035(2) 0.0076(19) 0.0151(19) -0.003(2) C4 0.050(3) 0.083(4) 0.048(3) 0.010(3) 0.002(2) -0.015(3) C5 0.052(3) 0.059(3) 0.046(3) 0.002(2) 0.016(2) -0.008(2) C6 0.063(3) 0.051(3) 0.057(3) -0.014(2) 0.032(3) -0.006(2) C7 0.083(4) 0.071(4) 0.067(4) -0.026(3) 0.047(3) -0.024(3) C8 0.069(3) 0.077(4) 0.039(2) -0.012(2) 0.030(2) -0.028(3) C9 0.050(3) 0.066(3) 0.030(2) -0.006(2) 0.0109(19) -0.023(2) C10 0.060(3) 0.064(3) 0.047(3) 0.009(2) 0.013(2) -0.019(3) C11 0.063(3) 0.046(3) 0.069(3) 0.018(3) 0.019(3) -0.004(2) C12 0.051(3) 0.045(3) 0.060(3) 0.004(2) 0.016(2) -0.001(2) C13 0.036(2) 0.047(2) 0.035(2) 0.0002(18) 0.0110(17) -0.0068(18) C14 0.038(2) 0.051(3) 0.0273(19) -0.0014(17) 0.0070(16) -0.0091(19) C15 0.038(2) 0.045(2) 0.0314(19) -0.0005(17) 0.0082(17) 0.0042(18) C16 0.052(3) 0.055(3) 0.043(2) -0.005(2) 0.006(2) 0.011(2) C17 0.068(4) 0.069(4) 0.047(3) -0.017(3) 0.009(3) 0.000(3) C18 0.060(3) 0.108(5) 0.042(3) -0.025(3) -0.001(2) -0.004(3) C19 0.049(3) 0.119(6) 0.049(3) -0.017(3) -0.012(2) 0.023(3) C20 0.048(3) 0.071(3) 0.046(3) -0.009(2) 0.005(2) 0.016(3) C21 0.032(2) 0.043(2) 0.043(2) -0.0001(18) 0.0077(17) -0.0018(17) C22 0.041(2) 0.057(3) 0.043(2) 0.005(2) 0.0075(19) -0.005(2) C23 0.042(3) 0.070(4) 0.059(3) 0.005(3) -0.002(2) 0.001(2) C24 0.034(3) 0.087(4) 0.080(4) -0.015(3) 0.003(3) 0.006(3) C25 0.049(3) 0.127(6) 0.058(3) -0.007(4) 0.021(3) 0.004(3) C26 0.042(3) 0.090(4) 0.042(3) 0.004(3) 0.013(2) 0.006(3) C27 0.073(4) 0.092(5) 0.055(3) 0.021(3) -0.002(3) 0.013(4) C28 0.080(6) 0.276(15) 0.110(7) 0.056(8) 0.030(5) -0.064(8) _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 (isot ropic) 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 Pd C1 2.006(4) . ? Pd N 2.135(4) . ? Pd P 2.2010(12) . ? Pd Cl 2.3345(14) . ? P C21 1.795(4) . ? P C15 1.806(4) . ? P C13 1.816(4) . ? N C6 1.313(6) . ? N C14 1.381(6) . ? O1 C2 1.198(6) . ? O2 C2 1.331(6) . ? O2 C27 1.436(6) . ? O3 C5 1.198(6) . ? O4 C5 1.324(6) . ? O4 C28 1.436(8) . ? C1 C3 1.320(6) . ? C1 C2 1.483(6) . ? C3 C5 1.491(6) . ? C3 C4 1.508(7) . ? C6 C7 1.403(7) . ? C7 C8 1.342(9) . ? C8 C9 1.400(7) . ? C9 C10 1.402(8) . ? C9 C14 1.417(6) . ? C10 C11 1.348(8) . ? C11 C12 1.395(7) . ? C12 C13 1.377(7) . ? C13 C14 1.397(6) . ? C15 C16 1.383(6) . ? C15 C20 1.386(6) . ? C16 C17 1.382(7) . ? C17 C18 1.363(9) . ? C18 C19 1.369(9) . ? C19 C20 1.374(7) . ? C21 C26 1.379(6) . ? C21 C22 1.390(6) . ? C22 C23 1.377(7) . ? C23 C24 1.361(8) . ? C24 C25 1.363(9) . ? C25 C26 1.371(7) . ? 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 C1 Pd N 174.53(17) . . ? C1 Pd P 90.95(13) . . ? N Pd P 84.68(11) . . ? C1 Pd Cl 90.85(13) . . ? N Pd Cl 93.39(11) . . ? P Pd Cl 177.04(5) . . ? C21 P C15 108.0(2) . . ? C21 P C13 106.3(2) . . ? C15 P C13 104.5(2) . . ? C21 P Pd 117.76(15) . . ? C15 P Pd 117.44(15) . . ? C13 P Pd 101.18(15) . . ? C6 N C14 118.4(4) . . ? C6 N Pd 124.7(3) . . ? C14 N Pd 116.6(3) . . ? C2 O2 C27 116.0(4) . . ? C5 O4 C28 116.0(6) . . ? C3 C1 C2 123.6(4) . . ? C3 C1 Pd 123.2(3) . . ? C2 C1 Pd 113.1(3) . . ? O1 C2 O2 122.8(4) . . ? O1 C2 C1 124.0(4) . . ? O2 C2 C1 113.0(4) . . ? C1 C3 C5 119.4(4) . . ? C1 C3 C4 123.7(4) . . ? C5 C3 C4 116.9(4) . . ? O3 C5 O4 122.9(5) . . ? O3 C5 C3 125.6(5) . . ? O4 C5 C3 111.5(4) . . ? N C6 C7 122.9(5) . . ? C8 C7 C6 119.8(5) . . ? C7 C8 C9 119.9(5) . . ? C8 C9 C10 123.5(5) . . ? C8 C9 C14 117.9(5) . . ? C10 C9 C14 118.6(5) . . ? C11 C10 C9 120.7(5) . . ? C10 C11 C12 121.5(5) . . ? C13 C12 C11 119.3(5) . . ? C12 C13 C14 120.5(4) . . ? C12 C13 P 122.9(4) . . ? C14 C13 P 116.5(3) . . ? N C14 C13 119.6(4) . . ? N C14 C9 121.0(4) . . ? C13 C14 C9 119.3(4) . . ? C16 C15 C20 119.6(4) . . ? C16 C15 P 123.2(3) . . ? C20 C15 P 117.0(4) . . ? C17 C16 C15 120.1(5) . . ? C18 C17 C16 119.8(5) . . ? C17 C18 C19 120.4(5) . . ? C18 C19 C20 120.8(5) . . ? C19 C20 C15 119.3(5) . . ? C26 C21 C22 118.7(4) . . ? C26 C21 P 119.8(4) . . ? C22 C21 P 121.4(4) . . ? C23 C22 C21 119.8(5) . . ? C24 C23 C22 120.8(5) . . ? C23 C24 C25 119.6(5) . . ? C24 C25 C26 120.8(5) . . ? C25 C26 C21 120.3(5) . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.04 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.477 _refine_diff_density_min -0.653 _refine_diff_density_rms 0.094