Abstract
The phenylene-bridged bimetallic organolanthanide complexesp- bis{Cp''Ln[N(SiHMe2)2]2}phenylene (p-Ln2;Ln = Y, La, Cp'' = tetramethylcyclopentadienyl) and m-bis{Cp''La[N(SiHMe2)2]2}phenylene (m-La2) are investigated for possible Ln ··· Ln cooperative effects in hydroamination processes. These binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, aminoallenes, and conjugated aminodienes with turnover frequencies as high as 10 h-1 at 60 °C, as well as intermolecular hydroaminations with turnover frequencies as high as 0.4 h-1 at 90 °C. Substrates include those having both compressed and extended junctures between the C-C unsaturation and the -NH2 group, as well as those with multiple -NH2 groups or places of C-C unsaturation. Reactivity trends appear to be dominated by nonbonded repulsive interactions, resulting in catalytic activities following the general trend m-Ln2 <p-Ln2. Organolanthanide amide complexes are also shown to catalyze the prototropic isomerization of alkynes.
| Original language | English |
|---|---|
| Pages (from-to) | 2423-2440 |
| Number of pages | 18 |
| Journal | Organometallics |
| Volume | 28 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - Apr 27 2009 |
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ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Phenylene-bridged binuclear organolanthanide complexes as catalysts for intramolecular and intermolecular hydroamination. / Yuen, Holming F.; Marks, Tobin J.
In: Organometallics, Vol. 28, No. 8, 27.04.2009, p. 2423-2440.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Phenylene-bridged binuclear organolanthanide complexes as catalysts for intramolecular and intermolecular hydroamination
AU - Yuen, Holming F.
AU - Marks, Tobin J
PY - 2009/4/27
Y1 - 2009/4/27
N2 - The phenylene-bridged bimetallic organolanthanide complexesp- bis{Cp''Ln[N(SiHMe2)2]2}phenylene (p-Ln2;Ln = Y, La, Cp'' = tetramethylcyclopentadienyl) and m-bis{Cp''La[N(SiHMe2)2]2}phenylene (m-La2) are investigated for possible Ln ··· Ln cooperative effects in hydroamination processes. These binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, aminoallenes, and conjugated aminodienes with turnover frequencies as high as 10 h-1 at 60 °C, as well as intermolecular hydroaminations with turnover frequencies as high as 0.4 h-1 at 90 °C. Substrates include those having both compressed and extended junctures between the C-C unsaturation and the -NH2 group, as well as those with multiple -NH2 groups or places of C-C unsaturation. Reactivity trends appear to be dominated by nonbonded repulsive interactions, resulting in catalytic activities following the general trend m-Ln2
AB - The phenylene-bridged bimetallic organolanthanide complexesp- bis{Cp''Ln[N(SiHMe2)2]2}phenylene (p-Ln2;Ln = Y, La, Cp'' = tetramethylcyclopentadienyl) and m-bis{Cp''La[N(SiHMe2)2]2}phenylene (m-La2) are investigated for possible Ln ··· Ln cooperative effects in hydroamination processes. These binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, aminoallenes, and conjugated aminodienes with turnover frequencies as high as 10 h-1 at 60 °C, as well as intermolecular hydroaminations with turnover frequencies as high as 0.4 h-1 at 90 °C. Substrates include those having both compressed and extended junctures between the C-C unsaturation and the -NH2 group, as well as those with multiple -NH2 groups or places of C-C unsaturation. Reactivity trends appear to be dominated by nonbonded repulsive interactions, resulting in catalytic activities following the general trend m-Ln2
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U2 - 10.1021/om9000023
DO - 10.1021/om9000023
M3 - Article
VL - 28
SP - 2423
EP - 2440
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -