- Bis(phosphinimino)methanide rare earth amides: Synthesis, structure, and catalysis of hydroamination/cyclization, hydrosilylation, and sequential hydroamination/hydrosilylation
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A series of yttrium and lanthanide amido complexes [Ln{N-(SiHMe 2)2}2{CH(PPh2NSiMe3) 2}] (Ln = Y, La, Sm, Ho, Lu) were synthesized by three different pathways. The title compounds can be obtained either from [Ln{N(SiHMe 2)2}3(thf)2] and [CH 2(PPh2NSiMe3)2] or from KN-(SiHMe2)2 and [Ln(CH(PPh2NSiMe 3)2}-Cl2]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh2NSiMe3)2}, LaCl3, and KN-(SiHMe2)2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe 2)2}2{CH(PPh2NSiMe3) 2}], were used as catalysts for hydroamination/cyclization and hydrosilylation reactions. A clear dependence of the reaction rate on the ionic radius of the center metal was observed, showing the lanthanum compound to be the most active one in both reactions. Furthermore, a combination of both reactions - a sequential hydroamination/hydrosilylation reaction - was also investigated.
- Rastaetter, Marcus,Zulys, Agustino,Roesky, Peter W.
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p. 3606 - 3616
(2008/02/10)
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- A bis(phosphinimino)methanide lanthanum amide as catalyst for the hydroamination/cyclisation, hydrosilylation and sequential hydroamination/ hydrosilylation catalysis
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[La{N(SiHMe2)2}2{CH(PPh 2NSiMe3)2}], which was obtained via an amine elimination starting from [CH2(PPh2NSiMe3) 2] and [La{N(SiHMe2)2}3(THF) 2], was used as catalyst for the hydroamination/cyclisation, the hydrosilylation and the sequential hydroamination/hydrosilylation reaction. The Royal Society of Chemistry 2006.
- Rastaetter, Marcus,Zulys, Agustino,Roesky, Peter W.
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p. 874 - 876
(2008/02/08)
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