5f3 vs. 4f3. Routes to and properties of highly reactive neodymium(III) hydrocarbyl and hydride complexes

Heiko Mauermann, Paul N. Swepston, Tobin J Marks

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109 Citations (Scopus)

Abstract

The reaction of Cp′2NdCl2-Li(ether)2 + (Cp′ = η5-(CH3)5C5) with LiCH [Si(CH3)3]2 yields the early lanthanide alkyl Cp′2NdCH[Si(CH3)3]2 (1). The molecular structure of this complex features an unusually short Nd-methyl contact. Reaction of 1 with hydrogen yields the highly reactive hydride (Cp′2NdH)2 (3). At 25°C, 1-atm gas pressure, 3 polymerizes ethylene with Nt, > 80 000 min-1 and hydrogenates 1-hexene with Nt = 77 000 h-1. Cyclohexene is hydrogenated with Nt = 8300 h-1. Kinetic measurements indicate that Nd-C hydrogenolysis is rate limiting for 1-hexene and that hydride + olefin addition is rate limiting for cyclohexene.

Original languageEnglish
Pages (from-to)200-202
Number of pages3
JournalOrganometallics
Volume4
Issue number1
Publication statusPublished - 1985

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Neodymium
hexenes
neodymium
Hydrides
hydrides
routes
hydrogenolysis
Lanthanoid Series Elements
Hydrogenolysis
Alkenes
Ether
Molecular structure
alkenes
gas pressure
Hydrogen
ethers
ethylene
molecular structure
Gases
Kinetics

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

5f3 vs. 4f3. Routes to and properties of highly reactive neodymium(III) hydrocarbyl and hydride complexes. / Mauermann, Heiko; Swepston, Paul N.; Marks, Tobin J.

In: Organometallics, Vol. 4, No. 1, 1985, p. 200-202.

Research output: Contribution to journalArticle

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N2 - The reaction of Cp′2NdCl2-Li(ether)2 + (Cp′ = η5-(CH3)5C5) with LiCH [Si(CH3)3]2 yields the early lanthanide alkyl Cp′2NdCH[Si(CH3)3]2 (1). The molecular structure of this complex features an unusually short Nd-methyl contact. Reaction of 1 with hydrogen yields the highly reactive hydride (Cp′2NdH)2 (3). At 25°C, 1-atm gas pressure, 3 polymerizes ethylene with Nt, > 80 000 min-1 and hydrogenates 1-hexene with Nt = 77 000 h-1. Cyclohexene is hydrogenated with Nt = 8300 h-1. Kinetic measurements indicate that Nd-C hydrogenolysis is rate limiting for 1-hexene and that hydride + olefin addition is rate limiting for cyclohexene.

AB - The reaction of Cp′2NdCl2-Li(ether)2 + (Cp′ = η5-(CH3)5C5) with LiCH [Si(CH3)3]2 yields the early lanthanide alkyl Cp′2NdCH[Si(CH3)3]2 (1). The molecular structure of this complex features an unusually short Nd-methyl contact. Reaction of 1 with hydrogen yields the highly reactive hydride (Cp′2NdH)2 (3). At 25°C, 1-atm gas pressure, 3 polymerizes ethylene with Nt, > 80 000 min-1 and hydrogenates 1-hexene with Nt = 77 000 h-1. Cyclohexene is hydrogenated with Nt = 8300 h-1. Kinetic measurements indicate that Nd-C hydrogenolysis is rate limiting for 1-hexene and that hydride + olefin addition is rate limiting for cyclohexene.

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