Mechanistic Insight into Protonolysis and Cis-Trans Isomerization of Benzylplatinum(II) Complexes Assisted by Weak Ligand-to-Metal Interactions. A Combined Kinetic and DFT Study
Emanuela Guido; Giuseppina D'Amico; Nino Russo; Emilia Sicilia; Silvia Rizzato; Alberto Albinati; Andrea Romeo; M. Rosaria Plutino; Raffaello Romeo; Inorganic Chemistry 50 (2011) 2224–2239; doi:10.1021/ic101879s

data_4324591
_publ_contact_author_address
;
 ISMN - CNR
 Unita' di Messina - Sezione di Palermo
 c/0 Dipartimento CICACF 
 Universita' di Messina
 Salita Sperone,31
 Vill. S. Agata - 98166 Messina,
 Italy
;
_publ_contact_author_email       rosaria.plutino@pa.ismn.cnr.it
_publ_contact_author_name        'R. Plutino'
_publ_section_title
;
 Mechanistic Insight into Protonolysis and Cis-Trans Isomerization of
 Benzylplatinum(II) Complexes Assisted by Weak Ligand-to-Metal
 Interactions. A Combined Kinetic and DFT Study
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              2224
_journal_page_last               2239
_journal_paper_doi               10.1021/ic101879s
_journal_volume                  50
_journal_year                    2011
_chemical_formula_sum            'C26 H42 Cl2 P2 Pt'
_chemical_formula_weight         682.53
_chemical_name_common            cis-[Pt(CH2C6H4Cl)2(PEt3)2]
_space_group_IT_number           9
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_version      2.4
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90.00
_cell_angle_beta                 120.802(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.5916(13)
_cell_length_b                   31.223(3)
_cell_length_c                   8.4416(9)
_cell_measurement_reflns_used    948
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      25.96
_cell_measurement_theta_min      2.53
_cell_volume                     2850.7(5)
_computing_cell_refinement       'SAINTPLUS  (Bruker AXS, 1999)'
_computing_data_collection       'SMART      (Bruker AXS, 2001)'
_computing_data_reduction        'SAINTPLUS  (Bruker AXS, 1999)'
_computing_molecular_graphics
'ORTEP for Windows v1.074 (L.J. Farrugia 1997)'
_computing_publication_material
'WinGX v1.64.05(L.J. Farrugia,J. Appl. Cryst.,1999,32, 837)'
_computing_structure_refinement  'SHELXL-97 (Acta Cryst.,2008,A64,112)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      295(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART CCD'
_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  0.0286
_diffrn_reflns_av_sigmaI/netI    0.0389
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            12487
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         1.99
_exptl_absorpt_coefficient_mu    5.234
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59436
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'Sadabs 2.01 (Bruker AXS, 1999)'
_exptl_crystal_colour            'ligth yellow'
_exptl_crystal_density_diffrn    1.590
_exptl_crystal_description       needle
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.322
_refine_diff_density_min         -0.494
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.009(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         5573
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0270
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0346P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0601
_refine_ls_wR_factor_ref         0.0645
_reflns_number_gt                5000
_reflns_number_total             5573
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic101879s_si_002_1.cif
_cod_data_source_block           rom24
_cod_original_cell_volume        2850.6(5)
_cod_database_code               4324591