The isolation and purification of tris-2,2′-bipyridine complexes of ruthenium(II) containing unsymmetrical ligands

被引:73
作者
Fletcher, NC [1 ]
Nieuwenhuyzen, M [1 ]
Rainey, S [1 ]
机构
[1] Queens Univ Belfast, Sch Chem, Belfast BT9 5AG, Antrim, North Ireland
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 2001年 / 18期
关键词
D O I
10.1039/b104365j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Monomeric ruthenium(II) complexes [Ru(L)(3)](2+) containing unsymmetric bipyridine ligands [Where L = 5-methyl-2,2'-bipyridine (L-1). 5-ethyl-2.2'-bipyridine (L-2). 5-propyl-2,2'-bipyridine (L-3), 5-(2-methylpropyl)-2,2'-bipyridine (L-4). 5-(2.2-dimethylpropyl)-2,2'-bipyridine (L-5) or 5-(carbomethoxy)-2,2'-bipyridine (L-6)] have been studied and the meridional and facial isomers isolated by the use of cation-exchange column chromatography (SP Sephadex C-25) eluting with either sodium toluene-4-sulfonate or sodium hexanoate. The relative yield of the facial isomer was found to decrease with increasing steric bulk, preventing the isolation of fac-[Ru(L-5)(3)](2-). The two isomeric forms were characterized by H-1 NMR spectroscopy. with the complexes [Ru(L1-3)(3)](2+) demonstrating an unusually large coupling between the H-6 and H-4 protons. Crystals suitable for X-ray structural analysis of [Ru(L-1)(3)](2+) were obtained as a mixture of the meridional and facial isomers, indicating that separation of this isomeric mixture could not be achieved by fractional crystallisation. The optical isomers of the complex [Ru(L-3)(3)](2+) were chromatographically separated on SP Sephadex C-25 relying upon the inherent chirality of the support. It is apparent that chiral interactions can inhibit geometric isomer separation using this technique.
引用
收藏
页码:2641 / 2648
页数:8
相关论文
共 37 条
[1]   BLACK MLCT ABSORBERS [J].
ANDERSON, PA ;
STROUSE, GF ;
TREADWAY, JA ;
KEENE, FR ;
MEYER, TJ .
INORGANIC CHEMISTRY, 1994, 33 (18) :3863-3864
[2]   BOTTOM-UP STRATEGY TO OBTAIN LUMINESCENT AND REDOX-ACTIVE METAL-COMPLEXES OF NANOMETRIC DIMENSIONS [J].
BALZANI, V ;
CAMPAGNA, S ;
DENTI, G ;
JURIS, A ;
SERRONI, S ;
VENTURI, M .
COORDINATION CHEMISTRY REVIEWS, 1994, 132 :1-13
[3]   Luminescent and redox-active polynuclear transition metal complexes [J].
Balzani, V ;
Juris, A ;
Venturi, M ;
Campagna, S ;
Serroni, S .
CHEMICAL REVIEWS, 1996, 96 (02) :759-833
[4]  
Balzani V.S. F., 1991, Supramolecular Photochemistry
[5]   CRYSTAL AND MOLECULAR-STRUCTURES OF [RU(BPY)3](PF6)3 AND [RU(BPY)3](PF6)2 AT 105-K [J].
BINER, M ;
BURGI, HB ;
LUDI, A ;
ROHR, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5197-5203
[6]   IMPROVED SYNTHESIS OF "4,4'-DISUBSTITUTED-2,2'-BIPYRIDINES [J].
BOS, KD ;
KRAAIJKAMP, JG ;
NOLTES, JG .
SYNTHETIC COMMUNICATIONS, 1979, 9 (06) :497-504
[7]   RUTHENIUM NMR-SPECTROSCOPY - A PROMISING STRUCTURAL AND ANALYTICAL TOOL - GENERAL TRENDS AND APPLICABILITY TO ORGANOMETALLIC AND INORGANIC-CHEMISTRY [J].
BREVARD, C ;
GRANGER, P .
INORGANIC CHEMISTRY, 1983, 22 (03) :532-535
[8]  
*BRUK, 1998, SAINT NT
[9]   LUMINESCENT METAL-COMPLEXES .4. C-13 NMR-SPECTRA OF THE TRIS CHELATES OF SUBSTITUTED 2,2'-BIPYRIDYLS AND 1,10-PHENANTHROLINES WITH RUTHENIUM(II) AND OSMIUM(II) [J].
COOK, MJ ;
LEWIS, AP ;
MCAULIFFE, GSG .
ORGANIC MAGNETIC RESONANCE, 1984, 22 (06) :388-394
[10]  
COOK MJ, 1982, INORG CHIM ACTA, V64, P25