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

Fingerprint

Actinoid Series Elements
Actinides
Carbon Monoxide
Thermodynamics
Hydrides
Carbon monoxide
Hydrogen
Hydrogen bonds
Carbon
Chemical activation
Nuclear magnetic resonance
Thorium
Infrared radiation
Carbonylation
Kinetics
Foster Home Care
Metals
Oxygen
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{1ff106be1ae04c908892279dceff7968,
title = "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.",
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.",
author = "Moloy, {Kenneth G.} and Marks, {Tobin J}",
year = "1984",
month = "1",
day = "1",
language = "English",
volume = "106",
pages = "7051--7064",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - 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.

AU - Moloy, Kenneth G.

AU - Marks, Tobin J

PY - 1984/1/1

Y1 - 1984/1/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0021517292&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0021517292&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0021517292

VL - 106

SP - 7051

EP - 7064

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 23

ER -