Abstract
The synthesis of the chelating polymethylcyclopentadienyl ligand (CH3)2Si[(CH3)4C5] 22- is reported. Reaction with ThCl4 followed by alkylation yields the new, thermally stable thorium hydrocarbyls (CH3)2Si[(CH3)4C5] 2ThR2, R = n-C4H9, CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5. The R = CH2Si(CH3)3 complex has also been characterized by single-crystal X-ray diffraction. The most unusual feature of the molecular structure is the rather small (ring center of gravity)-Th-(ring center of gravity) angle of 118.4° and the rather large ring-ring dihedral angle of 105.4°. The hydrocarbyls undergo facile hydrogenolysis to yield the new thorium hydride {(CH3)2Si[(CH3)4C5] 2ThH2}x. The infrared spectrum of this hydride lacks terminal Th-H stretching transitions. The new hydride catalyzes olefin hydrogenation at turnover frequencies significantly in excess of those for {Th [(CH3)5C5]2H2} 2.
| Original language | English |
|---|---|
| Pages (from-to) | 819-821 |
| Number of pages | 3 |
| Journal | Organometallics |
| Volume | 3 |
| Issue number | 5 |
| Publication status | Published - 1984 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Manipulation of organoactinide coordinative unsaturation and stereochemistry. Properties of chelating bis(polymethylcyclopentadienyl) hydrocarbyls and hydrides. / Fendrick, Carol M.; Mintz, Eric A.; Schertz, Larry D.; Marks, Tobin J; Day, Victor W.
In: Organometallics, Vol. 3, No. 5, 1984, p. 819-821.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Manipulation of organoactinide coordinative unsaturation and stereochemistry. Properties of chelating bis(polymethylcyclopentadienyl) hydrocarbyls and hydrides
AU - Fendrick, Carol M.
AU - Mintz, Eric A.
AU - Schertz, Larry D.
AU - Marks, Tobin J
AU - Day, Victor W.
PY - 1984
Y1 - 1984
N2 - The synthesis of the chelating polymethylcyclopentadienyl ligand (CH3)2Si[(CH3)4C5] 22- is reported. Reaction with ThCl4 followed by alkylation yields the new, thermally stable thorium hydrocarbyls (CH3)2Si[(CH3)4C5] 2ThR2, R = n-C4H9, CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5. The R = CH2Si(CH3)3 complex has also been characterized by single-crystal X-ray diffraction. The most unusual feature of the molecular structure is the rather small (ring center of gravity)-Th-(ring center of gravity) angle of 118.4° and the rather large ring-ring dihedral angle of 105.4°. The hydrocarbyls undergo facile hydrogenolysis to yield the new thorium hydride {(CH3)2Si[(CH3)4C5] 2ThH2}x. The infrared spectrum of this hydride lacks terminal Th-H stretching transitions. The new hydride catalyzes olefin hydrogenation at turnover frequencies significantly in excess of those for {Th [(CH3)5C5]2H2} 2.
AB - The synthesis of the chelating polymethylcyclopentadienyl ligand (CH3)2Si[(CH3)4C5] 22- is reported. Reaction with ThCl4 followed by alkylation yields the new, thermally stable thorium hydrocarbyls (CH3)2Si[(CH3)4C5] 2ThR2, R = n-C4H9, CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5. The R = CH2Si(CH3)3 complex has also been characterized by single-crystal X-ray diffraction. The most unusual feature of the molecular structure is the rather small (ring center of gravity)-Th-(ring center of gravity) angle of 118.4° and the rather large ring-ring dihedral angle of 105.4°. The hydrocarbyls undergo facile hydrogenolysis to yield the new thorium hydride {(CH3)2Si[(CH3)4C5] 2ThH2}x. The infrared spectrum of this hydride lacks terminal Th-H stretching transitions. The new hydride catalyzes olefin hydrogenation at turnover frequencies significantly in excess of those for {Th [(CH3)5C5]2H2} 2.
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M3 - Article
VL - 3
SP - 819
EP - 821
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 5
ER -