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Titolo:
Transfer of ketyls from alkali metals to transition metals. Formation and diverse reactivities of d-block transition-metal ketyls
Autore:
Hou, ZM; Fujita, A; Koizumi, T; Yamazaki, H; Wakatsuki, Y;
Indirizzi:
Inst Phys & Chem Res, Wako, Saitama 3510198, Japan Inst Phys & Chem Res Wako Saitama Japan 3510198 o, Saitama 3510198, Japan Chuo Univ, Dept Appl Chem, Bunkyo Ku, Tokyo 1120003, Japan Chuo Univ Tokyo Japan 1120003 Appl Chem, Bunkyo Ku, Tokyo 1120003, Japan
Titolo Testata:
ORGANOMETALLICS
fascicolo: 10, volume: 18, anno: 1999,
pagine: 1979 - 1985
SICI:
0276-7333(19990510)18:10<1979:TOKFAM>2.0.ZU;2-R
Fonte:
ISI
Lingua:
ENG
Soggetto:
LOW-VALENT TITANIUM; CARBON-CARBON BONDS; COUPLING REACTIONS; STRUCTURAL CHARACTERIZATION; COMPLEXES; IRIDIUM; ACTIVATION; CHEMISTRY; REAGENTS; CYCLOBUTENONES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
56
Recensione:
Indirizzi per estratti:
Indirizzo: Hou, ZM Inst Phys & Chem Res, Hirosawa 2-1, Wako, Saitama 3510198, Japan Inst Phys & Chem Res Hirosawa 2-1 Wako Saitama Japan 3510198 Japan
Citazione:
Z.M. Hou et al., "Transfer of ketyls from alkali metals to transition metals. Formation and diverse reactivities of d-block transition-metal ketyls", ORGANOMETAL, 18(10), 1999, pp. 1979-1985

Abstract

This paper reports our studies on the preparation of d-block transition-metal ketyls via metathesis reactions of alkali-metal ketyls with transition-metal chlorides as well as via deprotonation of pinacols with a transition-metal base. The metathesis reaction of sodium fluorenone ketyl with (C5Me5)(2)ZrCl2 in THF gave the corresponding zirconium fluorenone ketyl complex (C5Me5)(2)Zr(OC13H8)Cl (1), which represents the first example of a structurally characterized d-block transition-metal ketyl complex. In the case of sodium benzophenone ketyl, further reaction between the ketyl radical and a C5Me5 ligand took place to give finally the zirconium bis(alkoxide) complex(eta(5)-C5Me5)(eta(5):eta(5)-C5Me4CH2C(Ph)(2)O)Zr(OCHPh2) (2). In contrast, the similar reaction of [(C5Me5)Ir(mu-Cl)Cl](2) with sodium fluorenone ketyl yielded the iridium carbonyl complex (C5Me5)Ir(CO)(C12H8) (5), as a result of decarbonylation of fluorenone. When [(C5Me5)Ir(mu-H)Cl](2) was used to react with sodium fluorenone or benzophenone ketyl, the dechlorination (reduction) product [(C5Me5)Ir(mu-H)](2) (8), together with fluorenone or benzophenone, formed selectively. The ketone-free 8 could be obtained in highyields by reaction of [(C5Me5)Ir(mu-H)Cl](2) with 2 equiv of K or Na in THF. The reaction of 1,2-bis(biphenyl-2,2'-diyl)ethane-1,2-diol (9) with the iridium imido complex (C5Me5)(IrNBu)-Bu-t in THF gave a mixture of 5 (30%) and 8 2(fluorenone) (30%). However, when the reaction was carried out in benzene, the pinacolate complex (C5Me5)Ir(O2C26H16) (10) was formed as a major product (73%) together with a small amount of 5 (9%) and 8 (13%).

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Documento generato il 09/04/20 alle ore 00:24:04