2004年10月
Neutral paddlewheel diruthenium complexes with tetracarboxylates of large pi-conjugated substituents: Facile one-pot synthesis, crystal structures, and electrochemical studies
INORGANIC CHEMISTRY
- ,
- 巻
- 43
- 号
- 20
- 開始ページ
- 6464
- 終了ページ
- 6472
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1021/ic0493752
- 出版者・発行元
- AMER CHEMICAL SOC
A one-pot reaction of a cationic diruthenium complex, [RU2II,(III)(O2CCH3)(4)(THF)(2)](BF4) with arylcarboxylic acids, ArCO2H, (PhCO2H = benzoic acid, NaPCO2H = 1-naphthoic acid, AntCO(2)H = 9-anthracenecarboxylic acid) in NDMA (NDMA = N,N-dimethylaniline) has led to isolation of neutral paddlewheel-type diruthenium complexes, [Ru-2(II)(O2CAr)(4)(THF)(2)] (Ar = Ph (1), Nap (2), Ant (3)). Paramagnetic variable temperature (VT) H-1 NMR studies and GC-MS studies show that the reaction consists of two steps: a one-electron reduction of the Ru-2 core by NDMA and a simple carboxylate-exchange reaction. All compounds 1-3 were structurally characterized by X-ray crystallography. While the structural features of the Ru-2 core are very similar in all the compounds, the dihedral angles between the carboxylate plane and the aromatic ring are larger with the expanding of aryl groups from phenyl to anthracene. The effect of pi-pi stacking leads to the formation of a 1-D chain structure in compound 3, whereas compounds 1 and 2 are fully isolated from each other. The electrochemical measurements show that the quasireversible one-electron oxidation step is observed at +0.06, +0.09, and +0.17 V (vs Ag/Ag+) for 1-3, respectively, assigned to the Ru-2(II)/Ru-2(II,III) redox couple. These potentials are found to demonstrate a linear relationship with the substituent constants for aryl compounds, sigma(pi,B)(-).
- リンク情報
- ID情報
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- DOI : 10.1021/ic0493752
- ISSN : 0020-1669
- ORCIDのPut Code : 48612421
- Web of Science ID : WOS:000224181900049