The electronic structure of Ru(III)-ammine complexes and the product distribution from solid-state thermal reaction.
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概要
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INDO-type UHF-MO calculations were carried out for Ru(III)-ammine complexes in order to investigate their electronic structures and bonding nature. It was revealed that the ground state of RuX(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP>(X=F, Cl, Br, or I) is the <SUP>2</SUP>E state and that that of <I>cis</I>-RuX<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB><SUP>+</SUP> is the <SUP>2</SUP>A<SUB>1</SUB> state; in RuX(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP>, the odd electron exists not on the d<SUB>xy</SUB> orbital but on the d<SUB>xz</SUB> or d<SUB>yz</SUB> orbital which interacts with the p<SUB>π</SUB> orbital of the halide ligand, and in <I>cis</I>-RuX<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB><SUP>+</SUP>, this electron exists not on the d<SUB>xz</SUB> or d<SUB>xy</SUB> orbital but on the d<SUB>yz</SUB> orbital which interacts with the p<SUB>π</SUB> orbitals of the two halide ligands. Concenring the bonding nature, the following results were obtained: (1) the strength of the Ru–NH<SUB>3</SUB> bond in these complexes increases in the order, <I>cis</I>-RuX<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB><SUP>+</SUP><RuX(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP><Ru(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>3+</SUP><Ru(NH<SUB>3</SUB>)<SUB>6</SUB><SUP>3+</SUP>; (2) in the aqua-ammine complex, the Ru–OH<SUB>2</SUB> bond is weaker than the Ru–NH<SUB>3</SUB> bond; and (3) in the halogeno-ammine complexes, the <I>trans</I>-Ru–NH<SUB>3</SUB> bond is weaker than the <I>cis</I>-Ru–NH<SUB>3</SUB> bond. MO calculations were also carried out for some distorted states of RuCl(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP> From these results, a discussion is presented on the relation between the thermal reaction product and the reaction mechanism; <I>cis</I>-RuCl<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB><SUP>+</SUP> is expected to be produced <I>via</I> an associative reaction mechanism, while the <I>trans</I>-form product is expected to result from a dissociative mechanism.
- 公益社団法人 日本化学会の論文
著者
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SAKAKI Shigeyoshi
Department of Applied Chemistry & Biochemistry, Faculty of Engineering, Kumamoto University
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Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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Kohata Susumu
Yatsushiro National College of Technology
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