Synthesis, structure, and electronic study of some group VII furoyl substituted complexes

• Published in: Journal of organometallic chemistry Vol. 696; no. 10; pp. 2220 - 2227
• Main Authors: Snyder, Chad A., Tice, Nathan C., Maddox, Jeremy B., Emberton, Eric D., Vanover, Eric S., Hinson, Daniel F., Jackson, Daniel C.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 15.05.2011; Elsevier
• Subjects: Biomass; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Electronic structure; Fulvenes; Furans; Physical Sciences; Pyridazines; Science & Technology; X-ray crystallography; Pyridazines; X-ray crystallography; Electronic structure; Furans; Biomass; Fulvenes; POLYMERS; MOLECULAR CALCULATIONS; EFFECTIVE CORE POTENTIALS; BIOLOGICAL EVALUATION
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2010.11.041

The reaction of fulvene 1 with TlOEt in THF affords [Tl{1,2-C 5H 3(COC 4H 3O) 2}] ( 2) in 60% yield. Treatment of 2 with [MBr(CO) 5] (M = Mn, Re) in benzene reflux gave [Mn{η 5-1,2-C 5H 3(COC 4H 3O) 2}(CO) 3] ( 3A) and [Re{η 5-1,2-C 5H 3(COC 4H 3O) 2}(CO) 3] ( 3B) in 61% and 66% yields, respectively. Diacyl complexes 3A and 3B were ring-closed to the pyridazine by treating with hydrazine hydrate in methanol at room temperature. Fulvene 1 and diacyl complexes 3A and 3B have been structurally characterized by X-ray crystallography. Additionally, the electronic structure of complexes 3A and 3B and their relaxed structures have been characterized with density functional calculations. Calculated vibrational frequencies are compared with the experimental characterizations. [Display omitted] ► Furoyl substituted fulvene characterized by X-ray crystallography. Enolic H atom shared equal distance between diacyl oxygen atoms. ► Diacyl complexes ( 3A and 3B) and pyridazyl complexes ( 4A and 4B) made in moderate-high yields. ► Diacyl complexes 3A and 3B structurally determined by X-ray crystallography. ► Diacyl complexes 3A and 3B characterized by DFT calculations.