New synthetic route to monocarbonyl polypyridyl complexes of ruthenium: their stereochemistry and reactivity
Fletcher, Nicholas C., and Keene, F. Richard (1998) New synthetic route to monocarbonyl polypyridyl complexes of ruthenium: their stereochemistry and reactivity. Dalton Transactions (14). pp. 2293-2301.
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A new photochemical synthetic route to species of the type [Ru(terpy)(pp)(CO)]²⁺ has been elaborated [terpy = 2,2'∶6',2"-tetrapyridine; pp = a bidentate α,α'-diimine ligand such as 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4'-dimethyl-2,2'-bipyridine (dmbpy) or 4-(2-methylpropyl)-2,2'-bipyridine (mpbpy)]. For the species [Ru(terpy)(mpbpy)(CO)]²⁺ containing the new unsymmetrically substituted ligand (mpbpy) the two possible geometric isomers were separated by cation-exchange chromatography. The carbonyl groups can readily be removed and the vacant site substituted with pyridine, triphenylphosphine and chloride, with retention of the stereochemistry at the metal centre. By the correct choice of monodentate ligand at the sixth co-ordination site, the MLCT absorption maximum in the electronic spectra can be shifted by up to 150 nm, and the Ruⁱⁱⁱ–Ruⁱⁱ redox couple by over 1 V.
|Item Type:||Article (Refereed Research - C1)|
|Keywords:||ray crystal-structure; carbon bond formation; diastereoisomeric forms; redox properties; oxidation; ligand; mononuclear; dinuclear; reduction; kinetics|
|Date Deposited:||10 Aug 2012 04:18|
|FoR Codes:||03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%|
|SEO Codes:||97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%|