# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 186/1724 # Formation and Gas Phase Fragmentation Reactions of Ligand Substitution # Products of Platinum(II) Complexes via Electrospray Ionization Tandem # Mass Spectrometry # # M. S. Styles, R. A. J. O'Hair, W. D. McFadyen, L. Tannous, R. J. Holmes # and R. W. Gable data_lt_1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Chloro(N1,N1,N4,N7,N7-pentamethyldiethylenetriamine)platinum(II) perchlorate ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H23 Cl2 N3 O4 Pt' _chemical_formula_weight 503.29 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' 'Cl' 'Cl' 0.1484 0.1585 '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 Tetragonal _symmetry_space_group_name_H-M I4/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y, x, z' 'y, -x, z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' '-x, -y, -z' 'x, y, -z' 'y, -x, -z' '-y, x, -z' '-x+1/2, -y+1/2, -z+1/2' 'x+1/2, y+1/2, -z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 13.125(2) _cell_length_b 13.125(2) _cell_length_c 19.049(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3281.5(9) _cell_formula_units_Z 8 _cell_measurement_temperature 293(1) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 16.4 _cell_measurement_theta_max 31.6 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 2.037 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1936 _exptl_absorpt_coefficient_mu 8.889 _exptl_absorpt_correction_type Gaussian _exptl_absorpt_process_details 'Sheldrick, 1976' _exptl_absorpt_correction_T_min 0.0969 _exptl_absorpt_correction_T_max 0.5878 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(1) _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 'Enraf-Nonius CAD4-MachS diffractometer' _diffrn_measurement_method \w:2\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 160 _diffrn_standards_decay_% none _diffrn_reflns_number 4557 _diffrn_reflns_av_R_equivalents 0.0320 _diffrn_reflns_av_sigmaI/netI 0.0267 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 26.96 _reflns_number_total 1848 _reflns_number_gt 1631 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD-4 Software (Enraf-Nonius, 1989)' _computing_cell_refinement 'CAD-4 Software' _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEPII (Johnson, 1976)' _computing_publication_material SHELXL _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 w=1/[\s^2^(Fo^2^)+(0.0408P)^2^+41.1750P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary patt _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment geom _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00281(13) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1848 _refine_ls_number_parameters 89 _refine_ls_number_restraints 14 _refine_ls_R_factor_all 0.0405 _refine_ls_R_factor_gt 0.0339 _refine_ls_wR_factor_ref 0.0927 _refine_ls_wR_factor_gt 0.0896 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.045 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Pt Pt 0.24551(2) 0.26562(3) 0.0000 0.03228(17) Uani 1 d S . . Cl1 Cl 0.4154(2) 0.2220(3) 0.0000 0.0658(8) Uani 1 d S . . N1 N 0.2375(5) 0.2813(5) 0.1078(3) 0.0492(15) Uani 1 d . . . C1 C 0.3013(8) 0.3698(7) 0.1283(5) 0.068(2) Uani 1 d . . . H1A H 0.2901 0.3853 0.1769 0.102 Uiso 1 calc R . . H1B H 0.2831 0.4277 0.1002 0.102 Uiso 1 calc R . . H1C H 0.3718 0.3537 0.1210 0.102 Uiso 1 calc R . . C2 C 0.2723(9) 0.1899(7) 0.1478(4) 0.074(3) Uani 1 d . . . H2A H 0.2574 0.1990 0.1968 0.111 Uiso 1 calc R . . H2B H 0.3444 0.1813 0.1417 0.111 Uiso 1 calc R . . H2C H 0.2374 0.1305 0.1308 0.111 Uiso 1 calc R . . C3 C 0.1281(8) 0.3012(7) 0.1255(5) 0.067(3) Uani 1 d . . . H3A H 0.1239 0.3417 0.1679 0.087 Uiso 1 calc R . . H3B H 0.0932 0.2372 0.1337 0.087 Uiso 1 calc R . . C4 C 0.0779(6) 0.3571(6) 0.0658(4) 0.0534(19) Uani 1 d . . . H4A H 0.0054 0.3638 0.0746 0.069 Uiso 1 calc R . . H4B H 0.1068 0.4248 0.0612 0.069 Uiso 1 calc R . . N2 N 0.0955(6) 0.2974(6) 0.0000 0.046(2) Uani 1 d S . . C5 C 0.0299(9) 0.2029(9) 0.0000 0.072(4) Uani 1 d S . . H5A H 0.0431 0.1642 -0.0418 0.108 Uiso 0.50 calc PR . . H5B H -0.0406 0.2222 0.0013 0.108 Uiso 1 calc SR . . H5C H 0.0457 0.1623 0.0405 0.108 Uiso 0.50 calc PR . . Cl2 Cl 0.0000 0.0000 0.1920(2) 0.0599(10) Uani 1 d SD . . O21 O 0.0000 0.0000 0.1165(3) 0.150 Uiso 1 d SD . . O22 O 0.005(12) 0.1031(7) 0.2168(4) 0.150 Uiso 0.25 d PD . . O23 O 0.086(7) -0.057(10) 0.2168(4) 0.150 Uiso 0.25 d PD . . O24 O -0.092(5) -0.046(11) 0.2168(4) 0.150 Uiso 0.25 d PD . . Cl3 Cl 0.5000 0.0000 0.2500 0.0573(10) Uani 1 d SD . . O3 O 0.5825(5) 0.0340(10) 0.29344(17) 0.167(5) Uiso 1 d D . . 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 0.0325(2) 0.0357(2) 0.0287(2) 0.000 0.000 0.00380(13) Cl1 0.0369(13) 0.094(2) 0.0669(19) 0.000 0.000 0.0183(14) N1 0.071(4) 0.045(3) 0.032(3) -0.001(3) 0.003(3) 0.012(3) C1 0.091(7) 0.066(5) 0.047(5) -0.015(4) -0.016(5) 0.006(5) C2 0.126(9) 0.064(5) 0.033(4) 0.009(4) 0.001(5) 0.033(6) C3 0.083(6) 0.055(5) 0.062(6) 0.004(4) 0.032(5) 0.015(4) C4 0.048(4) 0.048(4) 0.064(5) -0.002(4) 0.022(4) 0.009(3) N2 0.033(4) 0.038(4) 0.066(6) 0.000 0.000 0.000(3) C5 0.040(6) 0.051(7) 0.126(13) 0.000 0.000 -0.012(5) Cl2 0.0615(14) 0.0615(14) 0.057(2) 0.000 0.000 0.000 Cl3 0.0645(14) 0.0645(14) 0.043(2) 0.000 0.000 0.000 _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 N2 2.013(8) . y Pt N1 2.067(6) 10 ? Pt N1 2.067(6) . y Pt Cl1 2.302(3) . y N1 C1 1.483(11) . y N1 C2 1.493(10) . y N1 C3 1.497(11) . y C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 H2A 0.9600 . ? C2 H2B 0.9600 . ? C2 H2C 0.9600 . ? C3 C4 1.504(12) . y C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 N2 1.496(9) . y C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? N2 C4 1.496(9) 10 ? N2 C5 1.509(13) . y C5 H5A 0.9600 . ? C5 H5B 0.9600 . ? C5 H5C 0.9600 . ? Cl2 O23 1.433(4) . ? Cl2 O22 1.435(4) . ? Cl2 O24 1.437(4) . ? Cl2 O21 1.438(5) . ? Cl3 O3 1.434(3) . ? Cl3 O3 1.434(3) 15 ? Cl3 O3 1.434(3) 2_655 ? Cl3 O3 1.434(3) 16_545 ? 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 N2 Pt N1 85.96(18) . 10 ? N2 Pt N1 85.96(18) . . y N1 Pt N1 167.2(3) 10 . y N2 Pt Cl1 177.6(2) . . y N1 Pt Cl1 94.25(18) 10 . ? N1 Pt Cl1 94.25(18) . . y C1 N1 C2 108.8(7) . . y C1 N1 C3 110.2(6) . . y C2 N1 C3 108.6(7) . . y C1 N1 Pt 108.1(5) . . y C2 N1 Pt 114.3(5) . . y C3 N1 Pt 106.8(5) . . y N1 C1 H1A 109.5 . . ? N1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? N1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 H2A 109.5 . . ? N1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? N1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? N1 C3 C4 109.6(7) . . y N1 C3 H3A 109.7 . . ? C4 C3 H3A 109.7 . . ? N1 C3 H3B 109.7 . . ? C4 C3 H3B 109.7 . . ? H3A C3 H3B 108.2 . . ? N2 C4 C3 108.1(6) . . y N2 C4 H4A 110.1 . . ? C3 C4 H4A 110.1 . . ? N2 C4 H4B 110.1 . . ? C3 C4 H4B 110.1 . . ? H4A C4 H4B 108.4 . . ? C4 N2 C4 113.9(8) 10 . y C4 N2 C5 110.0(5) 10 . ? C4 N2 C5 110.0(5) . . y C4 N2 Pt 105.0(5) 10 . ? C4 N2 Pt 105.0(5) . . y C5 N2 Pt 112.8(7) . . y N2 C5 H5A 109.5 . . ? N2 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? N2 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? O23 Cl2 O22 110.0(4) . . ? O23 Cl2 O24 109.7(4) . . ? O22 Cl2 O24 109.4(4) . . ? O23 Cl2 O21 109.3(2) . . ? O22 Cl2 O21 109.3(2) . . ? O24 Cl2 O21 109.2(2) . . ? O3 Cl3 O3 109.44(14) . 15 ? O3 Cl3 O3 109.5(3) . 2_655 ? O3 Cl3 O3 109.44(14) 15 2_655 ? O3 Cl3 O3 109.44(14) . 16_545 ? O3 Cl3 O3 109.5(3) 15 16_545 ? O3 Cl3 O3 109.44(14) 2_655 16_545 ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 Pt N1 C1 -115.7(6) . . . . ? N1 Pt N1 C1 -64.5(19) 10 . . . ? Cl1 Pt N1 C1 66.7(5) . . . . ? N2 Pt N1 C2 122.9(6) . . . . ? N1 Pt N1 C2 174.1(14) 10 . . . ? Cl1 Pt N1 C2 -54.6(6) . . . . ? N2 Pt N1 C3 2.8(5) . . . . ? N1 Pt N1 C3 54.0(19) 10 . . . ? Cl1 Pt N1 C3 -174.7(5) . . . . ? C1 N1 C3 C4 86.6(9) . . . . ? C2 N1 C3 C4 -154.3(7) . . . . ? Pt N1 C3 C4 -30.5(8) . . . . ? N1 C3 C4 N2 53.6(9) . . . . ? C3 C4 N2 C4 -162.7(6) . . . 10 ? C3 C4 N2 C5 73.3(9) . . . . ? C3 C4 N2 Pt -48.4(7) . . . . ? N1 Pt N2 C4 -24.8(5) 10 . . 10 ? N1 Pt N2 C4 145.2(5) . . . 10 ? Cl1 Pt N2 C4 -119.8(5) . . . 10 ? N1 Pt N2 C4 -145.2(5) 10 . . . ? N1 Pt N2 C4 24.8(5) . . . . ? Cl1 Pt N2 C4 119.8(5) . . . . ? N1 Pt N2 C5 95.00(18) 10 . . . ? N1 Pt N2 C5 -95.00(18) . . . . ? Cl1 Pt N2 C5 0.0 . . . . ? _diffrn_measured_fraction_theta_max 0.499 _diffrn_reflns_theta_full 26.96 _diffrn_measured_fraction_theta_full 0.499 _refine_diff_density_max 1.359 _refine_diff_density_min -1.624 _refine_diff_density_rms 0.169 #===END