The First Open-Paddlewheel Structures in Diruthenium Chemistry: Examples of Intermediate Magnetic Behaviour between Low and High Spin in Ru25+ Species
✍ Scribed by M. Carmen Barral; Teresa Gallo; Santiago Herrero; Reyes Jiménez-Aparicio; M. Rosario Torres; Francisco A. Urbanos
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 534 KB
- Volume
- 13
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
Abstract
The reaction of [Ru~2~Cl(O~2~CMe)(DPhF)~3~] (DPhF=N,N′‐diphenylformamidinate) with aqueous HCl leads to the substitution of the acetate ligand to give the complex [Ru~2~Cl~2~(DPhF)~3~] (1). Similar reaction of [Ru~2~(O~2~CMe)(DPhF)~3~(H~2~O)]BF~4~ with aqueous HBr or HI produces [Ru~2~Br~2~(DPhF)~3~] (2), and [Ru~2~I~2~(DPhF)~3~] (3), respectively. The reaction of 1 with AgBF~4~ to form the highly unsaturated unit [Ru~2~(DPhF)~3~]^2+^, which is isolated as [Ru~2~(BF~4~)(DPhF)~3~(H~2~O)]BF~4~ (4), and Ru~2~(MeCN)~2~(DPhF)~3~~2~ (5), is also reported. The use of AgNO~3~ instead of AgBF~4~ leads to [Ru~2~(NO~3~)~2~(DPhF)~3~] (6). The magnetic behaviour of complexes 1–4 and 6 is intermediate between high‐ and low‐spin configurations. A relationship between the magnetic behaviour and the visible‐near‐infrared (Vis‐NIR) spectra is apparent. In addition, the crystal structure determinations of 2, 4⋅THF, and 6, have been carried out. Complexes 1–3, 5 and 6 are the first examples of open‐paddlewheel structures in diruthenium chemistry. The BF~4~^−^ bridging the metal centres in 4⋅THF is activated and forms very short RuF bonds.