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

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

Northwestern University

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

92 Citations (Scopus)

Abstract

The synthesis of the chelating polymethylcyclopentadienyl ligand (CH₃)₂Si[(CH₃)₄C₅] ₂^2- 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

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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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 › peer-review

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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.",

author = "Fendrick, {Carol M.} and Mintz, {Eric A.} and Schertz, {Larry D.} and Marks, {Tobin J} and Day, {Victor W.}",

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

Abstract

ASJC Scopus subject areas

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