Carbon Monoxide Activation by Organoactinides. Formyl Pathways In CO Homologation and Hydrogenation

Dean A. Katahira; Kenneth G. Moloy; Tobin Jay Marks

doi:10.1021/om00072a037

Carbon Monoxide Activation by Organoactinides. Formyl Pathways In CO Homologation and Hydrogenation

Dean A. Katahira, Kenneth G. Moloy, Tobin Jay Marks^*

^*Corresponding author for this work

Chemistry

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Abstract

The carbonylation of Th[(CH₃)₅C₅]₂(OR)H (R = CH[C(CH₃)₃]₂) to yield an enediolate, {Th-[(CH₃)₅C₅]₂OR}₂[cis-OC(H)==C(H)O-], or, in the presence of H₂, the methoxide Th[(CH₃)₅C₅]₂(OR)(OCH₃) is argued on the basis of chemical and kinetic evidence to involve rate-limiting attack of a carbene-like η²-formyl (Th(η²-OCH)) on a Th-H functionality to produce a ThOCH₂Th intermediate. The intermediate suffers subsequent carbonylation and rearrangement to yield the enediolate or hydrogenolysis to yield the methoxide.

Original language	English (US)
Pages (from-to)	1723-1726
Number of pages	4
Journal	Organometallics
Volume	1
Issue number	12
DOIs	https://doi.org/10.1021/om00072a037
State	Published - Jan 1 1982

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{1c37f06d43e447a4b09ca1bb3aa77888,

title = "Carbon Monoxide Activation by Organoactinides. Formyl Pathways In CO Homologation and Hydrogenation",

abstract = "The carbonylation of Th[(CH3)5C5]2(OR)H (R = CH[C(CH3)3]2) to yield an enediolate, {Th-[(CH3)5C5]2OR}2[cis-OC(H)==C(H)O-], or, in the presence of H2, the methoxide Th[(CH3)5C5]2(OR)(OCH3) is argued on the basis of chemical and kinetic evidence to involve rate-limiting attack of a carbene-like η2-formyl (Th(η2-OCH)) on a Th-H functionality to produce a ThOCH2Th intermediate. The intermediate suffers subsequent carbonylation and rearrangement to yield the enediolate or hydrogenolysis to yield the methoxide.",

author = "Katahira, {Dean A.} and Moloy, {Kenneth G.} and Marks, {Tobin Jay}",

year = "1982",

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volume = "1",

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journal = "Organometallics",

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T1 - Carbon Monoxide Activation by Organoactinides. Formyl Pathways In CO Homologation and Hydrogenation

AU - Katahira, Dean A.

AU - Moloy, Kenneth G.

AU - Marks, Tobin Jay

PY - 1982/1/1

Y1 - 1982/1/1

N2 - The carbonylation of Th[(CH3)5C5]2(OR)H (R = CH[C(CH3)3]2) to yield an enediolate, {Th-[(CH3)5C5]2OR}2[cis-OC(H)==C(H)O-], or, in the presence of H2, the methoxide Th[(CH3)5C5]2(OR)(OCH3) is argued on the basis of chemical and kinetic evidence to involve rate-limiting attack of a carbene-like η2-formyl (Th(η2-OCH)) on a Th-H functionality to produce a ThOCH2Th intermediate. The intermediate suffers subsequent carbonylation and rearrangement to yield the enediolate or hydrogenolysis to yield the methoxide.

AB - The carbonylation of Th[(CH3)5C5]2(OR)H (R = CH[C(CH3)3]2) to yield an enediolate, {Th-[(CH3)5C5]2OR}2[cis-OC(H)==C(H)O-], or, in the presence of H2, the methoxide Th[(CH3)5C5]2(OR)(OCH3) is argued on the basis of chemical and kinetic evidence to involve rate-limiting attack of a carbene-like η2-formyl (Th(η2-OCH)) on a Th-H functionality to produce a ThOCH2Th intermediate. The intermediate suffers subsequent carbonylation and rearrangement to yield the enediolate or hydrogenolysis to yield the methoxide.

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Carbon Monoxide Activation by Organoactinides. Formyl Pathways In CO Homologation and Hydrogenation

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