Alkyne exchange reactions of silylalkyne complexes of tantalum: Mechanistic investigation and its application in the preparation of new tantalum complexes having functional alkynes (PhC≡CR (R = COOMe, CONMe2))

Toshiyuki Oshiki, Atsushi Yamada, Kimio Kawai, Hirotaka Arimitsu, Kazuhiko Takai

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Abstract

Silylalkyne complexes of tantalum with the general formula TaCl 3(R1C≡CR2)L2 (1, R1 = R2 = SiMe3, L2 = DME; 2, R1 = SiMe3, R2 = Me, L2 = DME; 6, R1 = R2 = SiMe3, L = py; 7, R1 = SiMe3, R2 = Me, L = py) reacted with an internal alkyne to give corresponding alkyne complexes via an alkyne exchange reaction. These silylalkyne complexes were newly prepared and structurally characterized. Kinetic measurements revealed that the rates of the exchange reactions of the DME complexes 1 and 2 were first-order dependent on the concentration of the complex and the reaction proceeded via dissociative pathway. The exchange reaction rates of the bis(pyridine) complexes 6 and 7 were slower. In contrast to the DME complexes, the exchange reaction of 6 proceeded via an associative interchange pathway, and the exchange mechanism for 7 was an associative pathway. During the exchange, two pyridine ligands coordinated strongly to the tantalum center and the intermediate is proposed to be a bis(alkyne) complex. New tantalum complexes having functional alkynes (PhC≡CR (R = COOMe, CONMe2)) were prepared from the silylalkyne complexes via the alkyne exchange reaction.

Original languageEnglish
Pages (from-to)173-182
Number of pages10
JournalOrganometallics
Volume26
Issue number1
DOIs
Publication statusPublished - Jan 1 2007

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Tantalum
Alkynes
alkynes
tantalum
preparation
pyridines
Interchanges
Reaction rates
reaction kinetics
Ligands
ligands
Kinetics
kinetics

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "Alkyne exchange reactions of silylalkyne complexes of tantalum: Mechanistic investigation and its application in the preparation of new tantalum complexes having functional alkynes (PhC≡CR (R = COOMe, CONMe2))",
abstract = "Silylalkyne complexes of tantalum with the general formula TaCl 3(R1C≡CR2)L2 (1, R1 = R2 = SiMe3, L2 = DME; 2, R1 = SiMe3, R2 = Me, L2 = DME; 6, R1 = R2 = SiMe3, L = py; 7, R1 = SiMe3, R2 = Me, L = py) reacted with an internal alkyne to give corresponding alkyne complexes via an alkyne exchange reaction. These silylalkyne complexes were newly prepared and structurally characterized. Kinetic measurements revealed that the rates of the exchange reactions of the DME complexes 1 and 2 were first-order dependent on the concentration of the complex and the reaction proceeded via dissociative pathway. The exchange reaction rates of the bis(pyridine) complexes 6 and 7 were slower. In contrast to the DME complexes, the exchange reaction of 6 proceeded via an associative interchange pathway, and the exchange mechanism for 7 was an associative pathway. During the exchange, two pyridine ligands coordinated strongly to the tantalum center and the intermediate is proposed to be a bis(alkyne) complex. New tantalum complexes having functional alkynes (PhC≡CR (R = COOMe, CONMe2)) were prepared from the silylalkyne complexes via the alkyne exchange reaction.",
author = "Toshiyuki Oshiki and Atsushi Yamada and Kimio Kawai and Hirotaka Arimitsu and Kazuhiko Takai",
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T2 - Mechanistic investigation and its application in the preparation of new tantalum complexes having functional alkynes (PhC≡CR (R = COOMe, CONMe2))

AU - Oshiki, Toshiyuki

AU - Yamada, Atsushi

AU - Kawai, Kimio

AU - Arimitsu, Hirotaka

AU - Takai, Kazuhiko

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