Manipulation of Organoactlnlde Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bls(polymethylcyclopentadlenyl) Hydrocarbyls and Hydrides

Carol M. Fendrlck; Eric A. Mlntz; Larry D. Schertz; Tobin J. Marks; Victor W. Day

doi:10.1021/om00083a036

Manipulation of Organoactlnlde Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bls(polymethylcyclopentadlenyl) Hydrocarbyls and Hydrides

Carol M. Fendrlck, Eric A. Mlntz, Larry D. Schertz, Tobin J. Marks^*, Victor W. Day

^*Corresponding author for this work

Chemistry

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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[(C-H₃)₅C₅]₂H₂)}₂.

Original language	English (US)
Pages (from-to)	819-821
Number of pages	3
Journal	Organometallics
Volume	3
Issue number	5
DOIs	https://doi.org/10.1021/om00083a036
State	Published - May 1984

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{8feb2ddf7dcc486c98116e31d16a30eb,

title = "Manipulation of Organoactlnlde Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bls(polymethylcyclopentadlenyl) Hydrocarbyls and Hydrides",

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[(C-H3)5C5]2H2)}2.",

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

year = "1984",

month = may,

doi = "10.1021/om00083a036",

language = "English (US)",

volume = "3",

pages = "819--821",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "5",

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TY - JOUR

T1 - Manipulation of Organoactlnlde Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bls(polymethylcyclopentadlenyl) Hydrocarbyls and Hydrides

AU - Fendrlck, Carol M.

AU - Mlntz, Eric A.

AU - Schertz, Larry D.

AU - Marks, Tobin J.

AU - Day, Victor W.

PY - 1984/5

Y1 - 1984/5

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[(C-H3)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[(C-H3)5C5]2H2)}2.

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Manipulation of Organoactlnlde Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bls(polymethylcyclopentadlenyl) Hydrocarbyls and Hydrides

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