CARBON MONOXIDE ACTIVATION BY ORGANOACTINIDES. A COMPARATIVE SYNTHETIC, THERMODYNAMIC, KINETIC, AND MECHANISTIC INVESTIGATION OF MIGRATORY CO INSERTION INTO ACTINIDE-CARBON AND ACTINIDE-HYDROGEN BONDS TO YIELD eta **2-ACYLS AND eta **2-FORMYLS.

Kenneth G. Moloy, Tobin J Marks

Research output: Contribution to journalArticle

113 Citations (Scopus)

Abstract

The authors report on the synthesis, characterization, and carbon monoxide chemistry of a series of sterically hindered thorium alkyls and hydrides of the type Cp prime //2Th(R)(X) (Cp prime equals eta **5-C//5Me//5) where R equals H, D, Me, n-Bu, and CH//2-t-Bu and X equals OCH-t-Bu//2, OC//6H//3-2,6-t-Bu//2, and O-t-Bu. In additon, improved synthesis of the known complexes left bracket Cp prime //2Th( mu -H)(H) right bracket //2, Cp prime //2Th(O-t-Bu)(Cl) and Cp prime //2Th(CH//2-t-Bu((Cl) are presented. The alkyl complexes undergo facile, irreversible carbonylation to yield eta **2-acyls that were characterized by a variety of methods. Infrared and **1**3C NMR spectra of these complexes demonstrate that strong metal-(acyl)oxygen bonding takes place, fostering a pronounced carbene-like character. The hydrides undergo a rapid, reversible, migratory CO insertion to yield formyls that have been characterized spectroscopically at low temperature. Infrared and **1**3C NMR spectra of these species are quite similar to the corresponding acyls, suggesitng an analogus eta **2 structure.

Original languageEnglish
Pages (from-to)7051-7064
Number of pages14
JournalJournal of the American Chemical Society
Volume106
Issue number23
Publication statusPublished - Jan 1 1984

ASJC Scopus subject areas

  • Chemistry(all)

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