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Role of bridging diamine linkers on the rate of ligand substitution in a series of dinuclear PtII complexes

✍ Scribed by D. Jaganyi; V. M. Munisamy; D. Reddy

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
215 KB
Volume
38
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

A series of dinuclear platinum^II^ complexes of the type [{trans‐Pt(H~2~O)(NH~3~)~2~}~2~‐NH~2~(CH~2~)~n~H~2~N]^4+^ (where n = 2, 3, 4, and 6) were synthesized to investigate the influence of the bridging diamine linker on the reactivity of the platinum centers. The p__K__~a~ values were determined, and the rates of substitution of the aqua moieties by a series of neutral nucleophiles viz. thiourea, 1,3‐dimethyl‐2‐thiourea, and 1,1,3,3‐tetramethyl‐2‐thiourea were studied as a function of concentration and temperature. All reactions studied gave excellent fits to a single exponential and obeyed the simple rate law, k~obs~=k~2~[Nu]. Negative activation entropies support an associative mode of substitution. The results obtained suggest that the rate of substitution is definitely influenced by the length of the diamine chain, with the rate of substitution decreasing as the length of the diamine chain increases. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 202–210, 2006

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