1. Spectroscopy and electrochemistry of new 6,6'-disubstituted-4,4'-bipyrimidine molybdenum(O) and tungsten(O) tetracarbonyl complexes
- Author
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Ioachim, Elena and Hanan, Garry S.
- Subjects
Electrochemistry -- Analysis ,Molybdenum -- Spectra ,Molybdenum -- Chemical properties ,Absorption spectra -- Analysis - Abstract
A new family of tetracarbonyl molybdenum(0) and tungsten(0) complexes based on new 6,6'-disubstituted-4,4'-bipyrimidine ligands was synthesized and characterized. The visible region of the absorption spectrum of each complex is dominated by a metal-to-ligand charge transfer band significantly lower in energy than the corresponding transition in 2,2'-bipyridine tetracarbonyl metal complexes. The 6,6'-substituents create a larger n-electronic system in the substituted bipyrimidines and are consequently better [pi] acceptors than even the parent 4,4'-bipyrimidine. The absorption bands are shifted bathochromically with a decrease in solvent polarity. Key words: molybdenum and tungsten, nitrogen ligands, tetracarbonyl metal complexes, absorption spectroscopy, electrochemistry. Resume : Une nouvelle famille de complexes de type tetracarbonyle de molybdbne(0) et tungstene(0), a base des 4,4'-bipyrimidine substituees dans les positions-6,6', a ete synthdtisde et caractdrisee. Le spectre d'absorption dans la region du visible de chaque compose indique un deplacement vers le rouge pour la bande de transfert de charge metal-ligand compare a celui du complexe tetracarbonyle de 2,2'-bipyridine. Ceci demontre une meilleure delocalisation du systeme [pi]-electronique darts la bipyrimidine substitude qui rend ces ligands des meilleurs accepteurs [pi]. Cette bande d'absorption est deplacee bathochromiquement avec la diminution de la polarite du solvant. Mots cles : molybdenum et tungsten, ligands azotes, complexes metal-tetracarbonyle, spectroscopie d'absorption, electrochimie.
- Published
- 2005