Synthesis and platinum- and palladium-catalyzed reactions of benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene)

Akinobu Naka, Kazunari Yoshizawa, Songyun Kang, Tokio Yamabe, Mitsuo Ishikawa

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) (1) was synthesized in situ by the reaction of 1,2,4,5-tetrabromobenzene with magnesium in the presence of diethylfluorosilane in THF. The reaction of 1 with diphenylacetylene in the presence of a catalytic amount of (η2- ethylene)bis(triphenylphosphine)platinum(0) in refluxing benzene gave a 1:2 adduct, benzo[1,2:4,5]bis(1,1,4,4-tetraethyl-2,3-&phenyl-1,4- disilacyclohexa-2,5-diene) in 91% yield. Similar platinum(0)-catalyzed reaction of 1 with 3-hexyne and acetylene in refluxing benzene afforded the respective 1:2 adducts benzo[1,2:4,5]bis(disilacyclohexadiene) derivatives in excellent yields. Benzobis(disilacyclobutene) 1 also reacted with diphenylacetylene, 3-hexyne, and acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)-palladium(0) to give the corresponding 1:2 adducts in excellent yields. Computational analyses of benzo[1,2:4,5] bis(disilacyclobutene) and its 1:1 and 1:2 adducts with acetylene were carried out using the B3LYP density-functional-theory method; the structures of these compounds were shown to be planar. The Si-Si bond in the disilacyclobutene ring appeared from computations to be effectively cleaved by a platinum(0) complex.

Original languageEnglish
Pages (from-to)5830-5835
Number of pages6
JournalOrganometallics
Volume17
Issue number26
DOIs
Publication statusPublished - Dec 21 1998
Externally publishedYes

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Acetylene
Palladium
Platinum
adducts
palladium
platinum
acetylene
Benzene
synthesis
benzene
Magnesium
Density functional theory
dienes
Derivatives
magnesium
ethylene
density functional theory
rings
triphenylphosphine
biphenylacetylene

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Synthesis and platinum- and palladium-catalyzed reactions of benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene). / Naka, Akinobu; Yoshizawa, Kazunari; Kang, Songyun; Yamabe, Tokio; Ishikawa, Mitsuo.

In: Organometallics, Vol. 17, No. 26, 21.12.1998, p. 5830-5835.

Research output: Contribution to journalArticle

Naka, Akinobu ; Yoshizawa, Kazunari ; Kang, Songyun ; Yamabe, Tokio ; Ishikawa, Mitsuo. / Synthesis and platinum- and palladium-catalyzed reactions of benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene). In: Organometallics. 1998 ; Vol. 17, No. 26. pp. 5830-5835.
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abstract = "Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) (1) was synthesized in situ by the reaction of 1,2,4,5-tetrabromobenzene with magnesium in the presence of diethylfluorosilane in THF. The reaction of 1 with diphenylacetylene in the presence of a catalytic amount of (η2- ethylene)bis(triphenylphosphine)platinum(0) in refluxing benzene gave a 1:2 adduct, benzo[1,2:4,5]bis(1,1,4,4-tetraethyl-2,3-&phenyl-1,4- disilacyclohexa-2,5-diene) in 91{\%} yield. Similar platinum(0)-catalyzed reaction of 1 with 3-hexyne and acetylene in refluxing benzene afforded the respective 1:2 adducts benzo[1,2:4,5]bis(disilacyclohexadiene) derivatives in excellent yields. Benzobis(disilacyclobutene) 1 also reacted with diphenylacetylene, 3-hexyne, and acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)-palladium(0) to give the corresponding 1:2 adducts in excellent yields. Computational analyses of benzo[1,2:4,5] bis(disilacyclobutene) and its 1:1 and 1:2 adducts with acetylene were carried out using the B3LYP density-functional-theory method; the structures of these compounds were shown to be planar. The Si-Si bond in the disilacyclobutene ring appeared from computations to be effectively cleaved by a platinum(0) complex.",
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T1 - Synthesis and platinum- and palladium-catalyzed reactions of benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene)

AU - Naka, Akinobu

AU - Yoshizawa, Kazunari

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AU - Yamabe, Tokio

AU - Ishikawa, Mitsuo

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N2 - Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) (1) was synthesized in situ by the reaction of 1,2,4,5-tetrabromobenzene with magnesium in the presence of diethylfluorosilane in THF. The reaction of 1 with diphenylacetylene in the presence of a catalytic amount of (η2- ethylene)bis(triphenylphosphine)platinum(0) in refluxing benzene gave a 1:2 adduct, benzo[1,2:4,5]bis(1,1,4,4-tetraethyl-2,3-&phenyl-1,4- disilacyclohexa-2,5-diene) in 91% yield. Similar platinum(0)-catalyzed reaction of 1 with 3-hexyne and acetylene in refluxing benzene afforded the respective 1:2 adducts benzo[1,2:4,5]bis(disilacyclohexadiene) derivatives in excellent yields. Benzobis(disilacyclobutene) 1 also reacted with diphenylacetylene, 3-hexyne, and acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)-palladium(0) to give the corresponding 1:2 adducts in excellent yields. Computational analyses of benzo[1,2:4,5] bis(disilacyclobutene) and its 1:1 and 1:2 adducts with acetylene were carried out using the B3LYP density-functional-theory method; the structures of these compounds were shown to be planar. The Si-Si bond in the disilacyclobutene ring appeared from computations to be effectively cleaved by a platinum(0) complex.

AB - Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) (1) was synthesized in situ by the reaction of 1,2,4,5-tetrabromobenzene with magnesium in the presence of diethylfluorosilane in THF. The reaction of 1 with diphenylacetylene in the presence of a catalytic amount of (η2- ethylene)bis(triphenylphosphine)platinum(0) in refluxing benzene gave a 1:2 adduct, benzo[1,2:4,5]bis(1,1,4,4-tetraethyl-2,3-&phenyl-1,4- disilacyclohexa-2,5-diene) in 91% yield. Similar platinum(0)-catalyzed reaction of 1 with 3-hexyne and acetylene in refluxing benzene afforded the respective 1:2 adducts benzo[1,2:4,5]bis(disilacyclohexadiene) derivatives in excellent yields. Benzobis(disilacyclobutene) 1 also reacted with diphenylacetylene, 3-hexyne, and acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)-palladium(0) to give the corresponding 1:2 adducts in excellent yields. Computational analyses of benzo[1,2:4,5] bis(disilacyclobutene) and its 1:1 and 1:2 adducts with acetylene were carried out using the B3LYP density-functional-theory method; the structures of these compounds were shown to be planar. The Si-Si bond in the disilacyclobutene ring appeared from computations to be effectively cleaved by a platinum(0) complex.

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