Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Holming F. Yuen; Tobin J. Marks

doi:10.1021/om7008952

Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Holming F. Yuen, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

76 Scopus citations

Abstract

Using base-free Ln[N(SiHMe₂)₂]₃ complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η⁵-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe₂)₂]₂}phenylene [p-Ln₂] (Ln -Y, La, Lu) and m-bis{η⁵-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe₂)₂] ₂}phenylene [m-La₂] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h ^-1 at 60°C.

Original language	English (US)
Pages (from-to)	155-158
Number of pages	4
Journal	Organometallics
Volume	27
Issue number	2
DOIs	https://doi.org/10.1021/om7008952
State	Published - Jan 28 2008

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om7008952

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title = "Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes",

abstract = "Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.",

author = "Yuen, {Holming F.} and Marks, {Tobin J.}",

year = "2008",

month = jan,

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doi = "10.1021/om7008952",

language = "English (US)",

volume = "27",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

AU - Yuen, Holming F.

AU - Marks, Tobin J.

PY - 2008/1/28

Y1 - 2008/1/28

N2 - Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.

AB - Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.

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Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Abstract

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CCDC 679487: Experimental Crystal Structure Determination

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Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Abstract

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CCDC 679487: Experimental Crystal Structure Determination

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