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The First Open‐Paddlewheel Structures in Diruthenium Chemistry: Examples of Intermediate Magnetic Behaviour between Low and High Spin in Ru 2 5+ Species
Author(s) -
Barral M. Carmen,
Gallo Teresa,
Herrero Santiago,
JiménezAparicio Reyes,
Torres M. Rosario,
Urbanos Francisco A.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700494
Subject(s) - chemistry , aqueous solution , crystallography , crystal structure , ligand (biochemistry) , ruthenium , infrared spectroscopy , stereochemistry , catalysis , organic chemistry , biochemistry , receptor
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 ](BF 4 ) 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.