# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_contact_author 'Piero Leoni' _publ_contact_author_address ; Dipartimento di Chimica e Chimica Industriale Universit\`a di Pisa Via Risorgimento, 35 56126 Pisa Italy ; _publ_contact_author_email leoni@dcci.unipi.it _publ_requested_coeditor_name ? _publ_contact_letter ; ; #============================================================================ # 3. TITLE AND AUTHOR LIST _publ_section_title ; Structure and Protonation of the Bis-Ethylene Adduct [Pt(\m-t-PBu2)(\h^2^- CH~2~=CH~2~)]~2~. Pt-H-P Agostic Interaction and Proton Scrambling ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address 'Piero Leoni' ; Dipartimento di Chimica e Chimica Industriale Universit\`a di Pisa Via Risorgimento, 35 56126 Pisa Italy ; 'Fabio Marchetti' ; Dipartimento di Chimica e Chimica Industriale Universit\`a di Pisa Via Risorgimento, 35 56126 Pisa Italy ; 'Lorella Marchetti' ; Dipartimento di Chimica Universit\`a di Siena Via A. Moro 53100 Siena Italy ; 'Vincenzo Passarelli' ; Dipartimento di Chimica e Chimica Industriale Universit\`a di Pisa Via Risorgimento, 35 56126 Pisa Italy ; _publ_contact_author_name 'Piero Leoni' #============================================================================ data_plafet _database_code_depnum_ccdc_archive 'CCDC 236901' _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis-(Di-t-butylphosphido)-bis-(\h^2^-ethylene-platinum) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C20 H44 P2 Pt2' _chemical_formula_sum 'C20 H44 P2 Pt2' _chemical_formula_weight 736.67 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pt Pt -1.7033 8.3905 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.250(2) _cell_length_b 8.4061(14) _cell_length_c 9.9730(14) _cell_angle_alpha 95.405(16) _cell_angle_beta 99.22(2) _cell_angle_gamma 111.029(18) _cell_volume 628.6(2) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 32 _cell_measurement_theta_min 5.48 _cell_measurement_theta_max 16.77 _exptl_crystal_description Prism _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.946 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 350 _exptl_absorpt_coefficient_mu 11.244 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.0434 _exptl_absorpt_correction_T_max 0.3262 _exptl_absorpt_process_details ? loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1.00 -1.00 0.00 0.2500 -1.00 1.00 0.00 0.2500 0.00 0.00 1.00 0.0500 0.00 0.00 -1.00 0.0500 2.00 2.00 -1.00 0.2100 -2.00 -2.00 1.00 0.2100 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker P4' _diffrn_measurement_method '2\q/\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2669 _diffrn_reflns_av_R_equivalents 0.0340 _diffrn_reflns_av_sigmaI/netI 0.0331 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 1 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.10 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2168 _reflns_number_gt 1984 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'WINGX-1.64 (Farrugia, 2001)' _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. ; _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^)+(0.0618P)^2^+0.0000P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0189(17) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2168 _refine_ls_number_parameters 110 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0427 _refine_ls_R_factor_gt 0.0375 _refine_ls_wR_factor_ref 0.0886 _refine_ls_wR_factor_gt 0.0860 _refine_ls_goodness_of_fit_ref 1.095 _refine_ls_restrained_S_all 1.095 _refine_ls_shift/su_max 0.001 _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 Pt Pt 0.39343(4) 0.39653(3) 0.56673(3) 0.03410(19) Uani 1 1 d . . . P P 0.3677(3) 0.3555(3) 0.3328(2) 0.0377(5) Uani 1 1 d . . . C1 C 0.2816(15) 0.2936(13) 0.7280(11) 0.065(3) Uani 1 1 d . . . H1A H 0.3492 0.2453 0.7886 0.079 Uiso 1 1 calc R . . H1B H 0.2260 0.3587 0.7761 0.079 Uiso 1 1 calc R . . C2 C 0.1801(16) 0.1875(15) 0.6018(15) 0.081(4) Uani 1 1 d . . . H2A H 0.0623 0.1877 0.5720 0.097 Uiso 1 1 calc R . . H2B H 0.1856 0.0742 0.5846 0.097 Uiso 1 1 calc R . . C1P C 0.4209(14) 0.1728(12) 0.2546(11) 0.057(2) Uani 1 1 d . . . C2P C 0.1755(12) 0.3815(13) 0.2224(10) 0.054(2) Uani 1 1 d . . . C3P C 0.5855(17) 0.1793(16) 0.3510(16) 0.091(4) Uani 1 1 d . . . H3PA H 0.5618 0.1678 0.4414 0.136 Uiso 1 1 calc R . . H3PB H 0.6811 0.2877 0.3547 0.136 Uiso 1 1 calc R . . H3PC H 0.6182 0.0865 0.3179 0.136 Uiso 1 1 calc R . . C4P C 0.275(2) -0.0024(16) 0.252(2) 0.109(6) Uani 1 1 d . . . H4PA H 0.2500 -0.0115 0.3420 0.164 Uiso 1 1 calc R . . H4PB H 0.3128 -0.0928 0.2223 0.164 Uiso 1 1 calc R . . H4PC H 0.1691 -0.0129 0.1883 0.164 Uiso 1 1 calc R . . C5P C 0.462(3) 0.193(2) 0.1156(17) 0.120(7) Uani 1 1 d . . . H5PA H 0.3597 0.1908 0.0532 0.180 Uiso 1 1 calc R . . H5PB H 0.4954 0.1007 0.0825 0.180 Uiso 1 1 calc R . . H5PC H 0.5589 0.3018 0.1216 0.180 Uiso 1 1 calc R . . C6P C 0.0123(17) 0.212(2) 0.183(2) 0.116(6) Uani 1 1 d . . . H6PA H -0.0140 0.1651 0.2646 0.174 Uiso 1 1 calc R . . H6PB H 0.0359 0.1312 0.1224 0.174 Uiso 1 1 calc R . . H6PC H -0.0874 0.2339 0.1373 0.174 Uiso 1 1 calc R . . C7P C 0.220(2) 0.453(3) 0.0949(16) 0.124(7) Uani 1 1 d . . . H7PA H 0.3240 0.5574 0.1196 0.186 Uiso 1 1 calc R . . H7PB H 0.1222 0.4769 0.0481 0.186 Uiso 1 1 calc R . . H7PC H 0.2418 0.3697 0.0352 0.186 Uiso 1 1 calc R . . C8P C 0.1279(16) 0.5124(17) 0.3088(15) 0.088(4) Uani 1 1 d . . . H8PA H 0.2303 0.6181 0.3384 0.132 Uiso 1 1 calc R . . H8PB H 0.0898 0.4663 0.3880 0.132 Uiso 1 1 calc R . . H8PC H 0.0339 0.5349 0.2544 0.132 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 Pt 0.0338(2) 0.0329(2) 0.0327(2) 0.00741(12) 0.01003(13) 0.00744(14) P 0.0366(10) 0.0355(10) 0.0366(11) 0.0023(8) 0.0076(9) 0.0094(9) C1 0.073(7) 0.058(6) 0.058(6) 0.026(5) 0.038(6) 0.002(5) C2 0.067(7) 0.061(7) 0.106(11) 0.027(7) 0.040(7) 0.003(6) C1P 0.066(6) 0.044(5) 0.058(6) -0.013(4) 0.016(5) 0.021(5) C2P 0.042(5) 0.060(6) 0.047(5) 0.001(4) -0.006(4) 0.013(4) C3P 0.096(10) 0.075(8) 0.121(12) 0.001(8) 0.025(9) 0.058(8) C4P 0.116(13) 0.042(6) 0.148(16) -0.010(8) 0.037(11) 0.007(7) C5P 0.21(2) 0.108(12) 0.081(10) 0.007(9) 0.074(13) 0.088(13) C6P 0.045(7) 0.101(11) 0.161(17) -0.015(11) -0.023(8) 0.008(7) C7P 0.104(12) 0.23(2) 0.071(9) 0.078(12) 0.022(8) 0.092(14) C8P 0.073(8) 0.101(10) 0.097(10) 0.007(8) -0.003(7) 0.051(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 (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 Pt C1 2.086(8) . ? Pt C2 2.098(9) . ? Pt P 2.290(2) . ? Pt P 2.293(2) 2_666 ? Pt Pt 2.6230(8) 2_666 ? P C2P 1.874(9) . ? P C1P 1.878(9) . ? P Pt 2.293(2) 2_666 ? C1 C2 1.413(17) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C1P C5P 1.491(18) . ? C1P C3P 1.513(16) . ? C1P C4P 1.527(16) . ? C2P C7P 1.498(17) . ? C2P C6P 1.531(16) . ? C2P C8P 1.532(16) . ? C3P H3PA 0.9600 . ? C3P H3PB 0.9600 . ? C3P H3PC 0.9600 . ? C4P H4PA 0.9600 . ? C4P H4PB 0.9600 . ? C4P H4PC 0.9600 . ? C5P H5PA 0.9600 . ? C5P H5PB 0.9600 . ? C5P H5PC 0.9600 . ? C6P H6PA 0.9600 . ? C6P H6PB 0.9600 . ? C6P H6PC 0.9600 . ? C7P H7PA 0.9600 . ? C7P H7PB 0.9600 . ? C7P H7PC 0.9600 . ? C8P H8PA 0.9600 . ? C8P H8PB 0.9600 . ? C8P H8PC 0.9600 . ? 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 Pt C2 39.5(5) . . ? C1 Pt P 144.0(3) . . ? C2 Pt P 104.6(4) . . ? C1 Pt P 105.8(3) . 2_666 ? C2 Pt P 145.3(4) . 2_666 ? P Pt P 110.17(6) . 2_666 ? C1 Pt Pt 160.8(3) . 2_666 ? C2 Pt Pt 159.7(4) . 2_666 ? P Pt Pt 55.15(5) . 2_666 ? P Pt Pt 55.03(6) 2_666 2_666 ? C2P P C1P 112.5(5) . . ? C2P P Pt 118.3(3) . . ? C1P P Pt 117.2(4) . . ? C2P P Pt 116.9(3) . 2_666 ? C1P P Pt 116.0(3) . 2_666 ? Pt P Pt 69.83(6) . 2_666 ? C2 C1 Pt 70.7(6) . . ? C2 C1 H1A 116.5 . . ? Pt C1 H1A 116.5 . . ? C2 C1 H1B 116.5 . . ? Pt C1 H1B 116.5 . . ? H1A C1 H1B 113.5 . . ? C1 C2 Pt 69.8(5) . . ? C1 C2 H2A 116.7 . . ? Pt C2 H2A 116.7 . . ? C1 C2 H2B 116.7 . . ? Pt C2 H2B 116.7 . . ? H2A C2 H2B 113.7 . . ? C5P C1P C3P 108.3(12) . . ? C5P C1P C4P 111.3(12) . . ? C3P C1P C4P 107.2(11) . . ? C5P C1P P 112.7(9) . . ? C3P C1P P 105.3(7) . . ? C4P C1P P 111.7(9) . . ? C7P C2P C6P 109.6(12) . . ? C7P C2P C8P 107.4(11) . . ? C6P C2P C8P 108.1(11) . . ? C7P C2P P 112.9(9) . . ? C6P C2P P 112.0(9) . . ? C8P C2P P 106.5(7) . . ? C1P C3P H3PA 109.5 . . ? C1P C3P H3PB 109.5 . . ? H3PA C3P H3PB 109.5 . . ? C1P C3P H3PC 109.5 . . ? H3PA C3P H3PC 109.5 . . ? H3PB C3P H3PC 109.5 . . ? C1P C4P H4PA 109.5 . . ? C1P C4P H4PB 109.5 . . ? H4PA C4P H4PB 109.5 . . ? C1P C4P H4PC 109.5 . . ? H4PA C4P H4PC 109.5 . . ? H4PB C4P H4PC 109.5 . . ? C1P C5P H5PA 109.5 . . ? C1P C5P H5PB 109.5 . . ? H5PA C5P H5PB 109.5 . . ? C1P C5P H5PC 109.5 . . ? H5PA C5P H5PC 109.5 . . ? H5PB C5P H5PC 109.5 . . ? C2P C6P H6PA 109.5 . . ? C2P C6P H6PB 109.5 . . ? H6PA C6P H6PB 109.5 . . ? C2P C6P H6PC 109.5 . . ? H6PA C6P H6PC 109.5 . . ? H6PB C6P H6PC 109.5 . . ? C2P C7P H7PA 109.5 . . ? C2P C7P H7PB 109.5 . . ? H7PA C7P H7PB 109.5 . . ? C2P C7P H7PC 109.5 . . ? H7PA C7P H7PC 109.5 . . ? H7PB C7P H7PC 109.5 . . ? C2P C8P H8PA 109.5 . . ? C2P C8P H8PB 109.5 . . ? H8PA C8P H8PB 109.5 . . ? C2P C8P H8PC 109.5 . . ? H8PA C8P H8PC 109.5 . . ? H8PB C8P H8PC 109.5 . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 1.896 _refine_diff_density_min -1.832 _refine_diff_density_rms 0.253 #===END