Alkyl(amino)- and Alkyl(chloro)phosphanyl-Substituted Cyclopentadienyl Complexes of Titanium and Zirconium

✍ Scribed by Vasily V. Kotov; Evgeni V. Avtomonov; Jörg Sundermeyer; Klaus Harms; Dmitry A. Lemenovskii

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 573 KB
• Volume: 2002
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/1099-0682(200203)2002:3<678::aid-ejic678>3.0.co;2-3

✦ Synopsis

Phosphanyl-substituted cyclopentadienes of the type [R n Cp-PR(NR 1 R 2 /Cl)] (1-22) (R = Alk, Ar; R 1 , R 2 = H, Alk, Ar, SiR 3 ; R n Cp = tBuCp, Me 4 Cp, Ind, Me 6 Ind, Flu) can be synthesised by reaction of alkyldichlorophosphanes and alkyl(amino)chlorophosphanes with alkali metal cyclopentadienides. The method used is a general one and provides high isolated yields of the target compounds. The phosphanylcyclopentadienes can easily be deprotonated by strong bases (e.g. nBuLi, PhCH 2 K, Ph 2 CHK) and the potassium salts [R n Cp-PR(NR 1 R 2 )]K ( -28) are efficiently transmetallated by Me 3 SnCl. A subsequent reaction with TiCl 4 (L) 2 and ZrCl 4 (L) 2 (L = THF, tetrahydrothiophene, Me 3 P) affords new half-sandwich complexes [{Me 4 Cp-PtBu(NEt 2 )}TiCl 3 ] (36), [{Me 4 Cp-PtBu(NEt 2 )}TiCl 3 ] (37) and [{tBuCp-PtBu-(NEt 2 )}TiCl 3 ] (38) in moderate yields. The reaction of [tBuCp-PtBu(Cl)] (6) with TiCl 4 in the presence of Et 3 N at low temperature yields the half-sandwich complex