Ariyo Olusegun, Moses published the artcileUnderstanding the role of flexible alkyl-¦Á,¦Ø-diamine linkers on the substitution behavior of dinuclear trans-platinum(II) complexes: A kinetic and mechanistic study, Formula: C3H8N2S, the publication is Inorganica Chimica Acta (2021), 120420, database is CAplus.
An investigation of the role of flexible alkyl-¦Á,¦Ø-diamine linkers on the substitution behavior of dinuclear trans-platinum(II) complexes. The substitution reactions of four dinuclear trans-platinum(II) complexes viz. [[PtNH3Cl2]2-¦Ì-NH2(CH2)2NH2] (P12), [[PtNH3Cl2]2-¦Ì-NH2(CH2)3NH2] (P13), [[PtNH3Cl2]2-¦Ì-NH2(CH2)4NH2] (P14) and [[PtNH3Cl2]2-¦Ì-NH2(CH2)5NH2] (P15) with three neutral thiourea-based nucleophiles specifically: thiourea (TU), N-methyl-2-thiourea (MTU) and N,N-dimethyl-2-thiourea (DMTU) were studied quant. under pseudo-first-order condition as function of concentration and temperature by conventional UV-Visible and stopped-flow spectrophotometers. The ligand substitution reaction of the complexes proceeds in veritably three consecutive steps. Each step follows first-order kinetics with the resp. complex and nucleophile. The pseudo first order rate constants, kobs(1/2/3), for sequential substitution of the chlorido ligands, the ammine, and subsequent displacement of the linker obeyed the rate law: kobs(1/2/3) = k(1/2/3)[NU]. The ligand substitution reactions were driven by both electronic and steric factors. However, our findings revealed that upon the substitution of the chlorido ligands by the nucleophiles at the platinum centers, the ¦Ò-donor capacity via inductive effect of these electron-rich nucleophiles over compensate the steric strain imposed by the nucleophiles and by the alkanediamine linker at the substitution sites. Consequently, electronic factors governed the overall reaction pattern of these complexes. 195Pt NMR results confirmed the simultaneous substitution of all the chlorido ligands by thiourea-based nucleophiles, followed by the subsequent but successive displacement of the ammine groups and the flexible alkanediamine linker from the metal centers. The order of reactivity of the nucleophiles with the complexes decreases with the increase in steric bulk in the nucleophiles: TU > MTU > DMTU. The small pos. enthalpy and the large but neg. entropy confirm the associative mode of activation for all the studied complexes. Computational modeling using d. functional theory (DFT) calculations was employed to rationalize the kinetic trends.
Inorganica Chimica Acta published new progress about 6972-05-0. 6972-05-0 belongs to catalysis-chemistry, auxiliary class Thiourea,Amine,Aliphatic hydrocarbon chain,Amide, name is 1,1-Dimethylthiourea, and the molecular formula is C3H8N2S, Formula: C3H8N2S.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia