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Titolo:
Synthesis and coordination chemistry of chelate ligands containing cyclopentadienyl, indenyl and fluorenyl donors - Diastereoselectivity and NMR structure analysis
Autore:
Vogelgesang, J; Frick, A; Huttner, G; Kircher, P;
Indirizzi:
Univ Heidelberg, Inst Anorgan Chem, D-69120 Heidelberg, Germany Univ Heidelberg Heidelberg Germany D-69120 , D-69120 Heidelberg, Germany
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 4, , anno: 2001,
pagine: 949 - 971
SICI:
1434-1948(200104):4<949:SACCOC>2.0.ZU;2-A
Fonte:
ISI
Lingua:
ENG
Soggetto:
FUNCTIONALIZED TRIPOD-LIGANDS; COMPLEXES BEARING FLUORENYL; ANSA-ZIRCONOCENE; NEOPENTANE FRAMEWORK; CONFORMATION; DERIVATIVES; OCTAHYDROFLUORENYL; CATALYSIS; MOLECULE;
Keywords:
cyclopentadienes; tripodal ligands; NMR spectroscopy; distance geometry; ruthenium; phosphorus;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
52
Recensione:
Indirizzi per estratti:
Indirizzo: Vogelgesang, J Univ Heidelberg, Inst Anorgan Chem, Neuenheimer Feld 270, D-69120 Heidelberg, Germany Univ Heidelberg Neuenheimer Feld 270 HeidelbergGermany D-69120
Citazione:
J. Vogelgesang et al., "Synthesis and coordination chemistry of chelate ligands containing cyclopentadienyl, indenyl and fluorenyl donors - Diastereoselectivity and NMR structure analysis", EUR J INORG, (4), 2001, pp. 949-971

Abstract

The functionalised oxetane O(CH2)(2)C(CH2Br) (CH2OMs) (1) is transformed into tripod ligands ROCH2C(CH2PPh2)-(CH2PR'(2))(CH2Cp#) (R = H, SiMe3; R' = Ph, Et; Cp# = indenyl, fluorenyl) (4) in a few steps. Epichlorohydrin O(CH2)CH(CH2Cl) (5) allows for diastereoselective one-pot syntheses of the Cp-functionalised chelate ligands (Cp#CH2)C(H)OH(CH2PPh2) (Cp-# = Cp, indenyl, fluorenyl) (6). The SiMe3-protected derivatives of these ligands react with RuCl2(PPh3)(3) to produce (Me3SiOCH(CH2-eta (1)-PPh2) (CH2-eta (5)-Cp#)Ru(PPh3) (Cl)) (Cp# = Cp, indenyl) (15) with high diastereoselective preference. With the same starting material, tripod Ligands 4 form Me3SiOCH2C(CH2-eta(1)-PPh2)(CH2-eta (1)-PPh2)(CH2- eta (5)-Indenyl)RuCl (R = Ph, Et) (16). As shown by complete NMR spectroscopy based structure analyses (DG methods) of 16, the formation of 16 (R = Et) is diastereoselective. The only diastereomer which is observed is the one in which the PEt2, donor and the phenylene part of the indenyl ligand are juxtaposed. In addition to quantitative NMR spectroscopy structure analyses, traditional analytical techniques, including X-ray analyses, were used to confirm the results.

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Documento generato il 16/07/20 alle ore 19:50:07