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Comparative Study of Ruthenium(II) and Ruthenium(III) Complexes with the Ligand dmbpy (dmbpy = 4, 4′‐Dimethyl‐2, 2′‐bipyridine)
Author(s) -
Seok Won K.,
Ran Jo Myeong,
Kim Nayeon,
Yun Hoseop
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200014
Subject(s) - ruthenium , crystallography , ligand (biochemistry) , chemistry , cerium , dihedral angle , atom (system on chip) , hydrogen bond , inorganic chemistry , molecule , catalysis , organic chemistry , biochemistry , receptor , embedded system , computer science
The complex cis ‐[Ru III (dmbpy) 2 Cl 2 ](PF 6 ) ( 2 ) (dmbpy = 4, 4′‐dimethyl‐2, 2′‐bipyridine) was obtained from the reaction of cis ‐[Ru II (dmbpy) 2 Cl 2 ] ( 1 ) with ammonium cerium(IV) nitrate followed by precipitation with saturated ammonium hexafluoridophosphate. The 1 H NMR spectrum of the Ru III complex confirms the presence of paramagnetic metal atoms, whereas that of the Ru II complex displays diamagnetism. The 31 P NMR spectrum of the Ru III complex shows one signal for the phosphorus atom of the PF 6 – ion. The perspective view of each [Ru II/III (dmbpy) 2 Cl 2 ] 0/+ unit manifests that the ruthenium atom is in hexacoordinate arrangement with two dmbpy ligands and two chlorido ligands in cis position. As the oxidation state of the central ruthenium metal atom becomes higher, the average Ru–Cl bond length decreases whereas the Ru–N (dmbpy) bond length increases. The cis ‐positioned dichloro angle in Ru III is 1.3° wider than that in the Ru II . The dihedral angles between pair of planar six‐membered pyridyl ring in the dmbpy ligand for the Ru II are 4.7(5)° and 5.7(4)°. The observed inter‐planar angle between two dmbpy ligands in the Ru II is 89.08(15)°, whereas the value for the Ru III is 85.46(20)°.