Synthesis and Reactivity of Bis(phospholyl)neodymium(III) and -samarium(III) Chlorides and Alkyl Derivatives

✍ Scribed by François Nief; Philippe Riant; Louis Ricard; Pascale Desmurs; Denise Baudry-Barbier

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 255 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199906)1999:6<1041::aid-ejic1041>3.0.co;2-e

✦ Synopsis

The reaction of 2,3,4,5-tetramethylphospholylpotassium alkyl complexes [(C 4 Me 4 P) 2 LnCH(SiMe 3 ) 2 ]; these complexes were most efficiently prepared from [LnCl 3 (THF) x ], [C 4 Me 4 PK] with [LnCl 3 (THF) x ] (Ln = Nd, Sm) in a 2:1 ratio gave unsolvated ate complexes of the formula [KC 4 Me 4 P] and [LiCH(SiMe 3 ) 2 ] in a one-pot procedure. Reaction of [(C 4 Me 4 P) 2 LnCH(SiMe 3 ) 2 ] with molecular [(C 4 Me 4 P) 2 LnCl 2 K]. Crystallisation of the samarium complex from ether afforded a polymeric ether solvate: {[(η 5 -hydrogen gave [(C 4 Me 4 P) 2 NdH], when Ln = Nd, whereas, when Ln = Sm, reduction occurred and the already known C 4 Me 4 P)Sm(µ 3 -Cl) 2 (µ:η 5 ,η 1 -C 4 Me 4 P)K(Et 2 O)] ϱ }, which was characterised by X-ray crystallography. Reaction of [(C 4 Me 4 P) 2 Sm] was isolated instead. [(C 4 Me 4 P) 2 LnCl 2 K] with [LiCH(SiMe 3 ) 2 ] in toluene gave the lyl)neodymium and -samarium chlorides and alkyl deriva-[(C 4 Me 4 P) 2 NdCl 2 K] (2), respectively, on the following

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