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- W2043638342 abstract "Abstract Several platinum(II) complexes of the general type [Pt(OND)X] have been prepared and characterized, the ligand (OND) representing the phenolate anion of the tridentate Schiff bases N -(2- diethylaminoethyl)-salicylaldimine (D = NEt 2 ), N -(2- ethylaminoethyl)-salicylaldimine (D = NHEt) and N - (3-thia-n-pentyl)-salicylaldimine (D= SEt) and X= Cl, NO 3 . As shown by conductimetric studies the nitrato complexes [Pt(OND)NO 3 ] dissociate completely in methanol according to: Spectrophotometry (normal and stopped-flow) has been used to study the kinetics of solvent substitution according to with a variety of neutral and anionic nucleophiles Y in methanol at 20 °C and constant ionic strength, I = 0.2 M (NaClO 4 ). The substitution follows a one- term rate law, v = k obs [Pt(OND)(H 2 O) + ] = k Y [Y]- [Pt(OND)(H 2 O) + ]. The k Y data obtained for 13 (D = NEt 2 ) and 7 (D = NHEt; SEt) different nucleophiles Y cannot be adequately correlated with their n pt 0 values according to the well-known relationship log k Y = sn pt 0 + log k s . The deviations are strongest for large and bulky nucleophiles such as Y=Ph 3 P, Bu 3 P, Ph 3 As, I - and for D = NEt 2 , from which it is concluded that steric crowding hinders the formation of the 5-coordinate transition state. The rate reducing steric cis -effect observed is of the order k Y (D = NEt 2 ): k Y (D = NHEt): k Y (D = SEt) = 1:35:63 for small nucleophiles Y and as large as 1:192:2640 for Y = Ph 3 P. The introduction of substituents X in the salicylaldehyde ring in ortho (X 3 ), meta (X 4 ) and para position (X 5 ) to the phenolic oxygen proves the existence of rather small electronic effects (X 4 , X 5 ) and much stronger steric effects of bulky substituents X 3 , neighboring the donor oxygen. With the standard substrate trans -[Ptpy 2 Cl 2 ] some new n pt 0 values were determined, namely for N , N ′- dimethylthiourea ( n pt 0 = 7.02), N , N ′ -diphenylthlourea ( n pt 0 = 7.19), N , N , N ′, N ′-tetramethylthiourea ( n pt 0 = 6.05) and for the pseudo-halide dicyanoamide ion, N(CN) 2 - ( n pt 0 = 3.05). The n pt 0 value for the pseudo-halide tricyanomethanide, ion, C(CN) 3 - , was estimated to be 3.03." @default.
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- W2043638342 date "1986-06-01" @default.
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- W2043638342 title "Kinetics of ligand substitution in platinum(II) complexes: A study on the concept of nucleophilic discrimination" @default.
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- W2043638342 doi "https://doi.org/10.1016/s0020-1693(00)84620-4" @default.
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