NDLI: Titanium ferrocenyl-phosphinimide complexes

Content Provider	Royal Society of Chemistry (RSC)
Author	Ramos, Alberto Stephan, Douglas W.
Copyright Year	2010
Abstract	Oxidation of [CpFe(η5-C5H4PtBu2)] with Me3SiN3 gave the phosphinimine [CpFe(η5-C5H4PtBu2NSiMe3)] (1) which was used to prepare [Cp′TiCl2(NPtBu2C5H4)FeCp] (Cp′ = Cp 2, Cp* 4) and subsequently [Cp′TiMe2(NPtBu2C5H4)FeCp] (Cp′ = Cp 3, Cp* 5). Similarly, [(η5-C5Ph5)Fe(η5-C5H4PtBu2NSiMe3)] 6 was converted to [CpTiX2(NPtBu2C5H4)Fe(η5-C5Ph5)] (X = Cl 7, Me 8). The bis-phosphinimine [Fe{η5-C5H4PtBu2(NSiMe3)}2] (9) was prepared and used to obtain [{Fe(η5-C5H4PtBu2N)2}TiCl2] (10) and [{Fe(η5-C5H4PtBu2N)2}TiMe2] (11). These species exhibited a temperature dependent conformational change in the chelate geometry on the NMR time scale. Cyclic voltammetry studies showed pseudo reversible redox waves assigned to the Fe2+/Fe3+ couple for 2 and 4, while 10 exhibited only irreversible oxidations. Compound 9 was also used to prepare [Fe(η5-C5H4PtBu2NTiXCl2)2] (X = Cl 12, Cp 13, Cp* 15). Compounds 3 and 5 react with B(C6F5)3 or [CPh3][B(C6F5)3] to generate salts of the formula [Cp′TiMe{(NPtBu2C5H4)FeCp}]X (Cp′ = Cp, X = [MeB(C6F5)3] 17a, [B(C6F5)4] 17b; Cp′ = Cp, X = [MeB(C6F5)3] 18a, [B(C6F5)4] 18b). Compounds 18 further generated [CpTiMe{HNPtBu2(C5H4)Fe(η5,η1-C5H4)}]X (X = [MeB(C6F5)3] 19a, [B(C6F5)4] 19b), respectively. The cationic species 17a and 18a are very active polymerization catalysts, giving polyethylene with activities of 2400 and 5000 g mmol−1 h−1 atm−1, respectively at 25 °C.
Starting Page	1328
Ending Page	1338
Page Count	11
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	39
Issue Number	5
Journal	Dalton Transactions
DOI	10.1039/b918919j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Molecular geometry Nuclear magnetic resonance Cyclic voltammetry Redox Polymerization Polyethylene
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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