Manipulation of organoactinide coordinative unsaturation and stereochemistry. Properties of chelating bis(polymethylcyclopentadienyl) hydrocarbyls and hydrides

Carol M. Fendrick, Eric A. Mintz, Larry D. Schertz, Tobin J Marks, Victor W. Day

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)819-821
Number of pages3
JournalOrganometallics
Volume3
Issue number5
Publication statusPublished - 1984

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Stereochemistry
stereochemistry
Chelation
Hydrides
Thorium
hydrides
manipulators
center of gravity
rings
thorium
Gravitation
Hydrogenolysis
Alkylation
Alkenes
Dihedral angle
hydrogenolysis
Molecular structure
Hydrogenation
Stretching
alkylation

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 journalArticle

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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.",
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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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