5Cyclopentadienyl)- and (η5-Pentamethylcyclopentadienyl)copper Compounds Containing Phosphine, Carbonyl, and η2-Acetylenic Ligands

David W. Macomber, Marvin D. Rausch

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Abstract

The formation, spectra, and properties of a series of (η5-pentamethylcyclopentadienyl)copper compounds have been investigated. Reactions between lithium pentamethylcyclopentadienide and [C1Cu(R3P)]4 (R = C6H5, C2H5) produced [η5C5(CH3)5](PR3)Cu in yields of 43% and 78%, respectively. A reaction between lithium pentamethylcyclopentadienide and copper(I) chloride in ethyl ether solution in the presence of carbon monoxide led to [η5-C5(CH3)5](CO)Cu. This carbonyl derivative was both air- and temperature-sensitive and decomposed in solution over 0 ºC to afford copper metal, carbon monoxide, and decamethyl-1,1′-dihydrofulvalene. A reaction between copper(I) chloride and bis(trimethylsilyl)acetylene produced [η2-(CH3)3SiC==CSi(CH3)3]2Cu2Cl2 in 76% yield. Treatment of the latter dimer with lithium pentamethylcyclopentadienide in ethyl ether solution afforded [η5-C5(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu. The parent compound (η5-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu was also obtained starting with lithium cyclopentadienide. Both products were air- and temperature-sensitive but could be readily converted into the respective triphenylphosphine derivatives. The complexes [η5-C5-(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu and (η2-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu represent the first “mixed-sandwich compounds of copper, as predicted by the effective atomic number (EAN) rule.

Original languageEnglish (US)
Pages (from-to)5325-5329
Number of pages5
JournalJournal of the American Chemical Society
Volume105
Issue number16
DOIs
StatePublished - Jan 1 1983

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phosphine
Copper compounds
Lithium
Copper
Carbon Monoxide
Ligands
Carbon monoxide
Ether
Ethers
Air
Derivatives
Acetylene
Temperature
Dimers
Metals

Cite this

@article{6762815543ee46f99ee5deb3e3d42d0d,
title = "(η5Cyclopentadienyl)- and (η5-Pentamethylcyclopentadienyl)copper Compounds Containing Phosphine, Carbonyl, and η2-Acetylenic Ligands",
abstract = "The formation, spectra, and properties of a series of (η5-pentamethylcyclopentadienyl)copper compounds have been investigated. Reactions between lithium pentamethylcyclopentadienide and [C1Cu(R3P)]4 (R = C6H5, C2H5) produced [η5C5(CH3)5](PR3)Cu in yields of 43{\%} and 78{\%}, respectively. A reaction between lithium pentamethylcyclopentadienide and copper(I) chloride in ethyl ether solution in the presence of carbon monoxide led to [η5-C5(CH3)5](CO)Cu. This carbonyl derivative was both air- and temperature-sensitive and decomposed in solution over 0 ºC to afford copper metal, carbon monoxide, and decamethyl-1,1′-dihydrofulvalene. A reaction between copper(I) chloride and bis(trimethylsilyl)acetylene produced [η2-(CH3)3SiC==CSi(CH3)3]2Cu2Cl2 in 76{\%} yield. Treatment of the latter dimer with lithium pentamethylcyclopentadienide in ethyl ether solution afforded [η5-C5(CH3)5][η2-(CH3)3SiC=CS {\'i}(CH3)3]Cu. The parent compound (η5-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu was also obtained starting with lithium cyclopentadienide. Both products were air- and temperature-sensitive but could be readily converted into the respective triphenylphosphine derivatives. The complexes [η5-C5-(CH3)5][η2-(CH3)3SiC=CS {\'i}(CH3)3]Cu and (η2-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu represent the first “mixed-sandwich compounds of copper, as predicted by the effective atomic number (EAN) rule.",
author = "Macomber, {David W.} and Rausch, {Marvin D.}",
year = "1983",
month = "1",
day = "1",
doi = "10.1021/ja00354a023",
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volume = "105",
pages = "5325--5329",
journal = "Journal of the American Chemical Society",
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T1 - (η5Cyclopentadienyl)- and (η5-Pentamethylcyclopentadienyl)copper Compounds Containing Phosphine, Carbonyl, and η2-Acetylenic Ligands

AU - Macomber, David W.

AU - Rausch, Marvin D.

PY - 1983/1/1

Y1 - 1983/1/1

N2 - The formation, spectra, and properties of a series of (η5-pentamethylcyclopentadienyl)copper compounds have been investigated. Reactions between lithium pentamethylcyclopentadienide and [C1Cu(R3P)]4 (R = C6H5, C2H5) produced [η5C5(CH3)5](PR3)Cu in yields of 43% and 78%, respectively. A reaction between lithium pentamethylcyclopentadienide and copper(I) chloride in ethyl ether solution in the presence of carbon monoxide led to [η5-C5(CH3)5](CO)Cu. This carbonyl derivative was both air- and temperature-sensitive and decomposed in solution over 0 ºC to afford copper metal, carbon monoxide, and decamethyl-1,1′-dihydrofulvalene. A reaction between copper(I) chloride and bis(trimethylsilyl)acetylene produced [η2-(CH3)3SiC==CSi(CH3)3]2Cu2Cl2 in 76% yield. Treatment of the latter dimer with lithium pentamethylcyclopentadienide in ethyl ether solution afforded [η5-C5(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu. The parent compound (η5-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu was also obtained starting with lithium cyclopentadienide. Both products were air- and temperature-sensitive but could be readily converted into the respective triphenylphosphine derivatives. The complexes [η5-C5-(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu and (η2-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu represent the first “mixed-sandwich compounds of copper, as predicted by the effective atomic number (EAN) rule.

AB - The formation, spectra, and properties of a series of (η5-pentamethylcyclopentadienyl)copper compounds have been investigated. Reactions between lithium pentamethylcyclopentadienide and [C1Cu(R3P)]4 (R = C6H5, C2H5) produced [η5C5(CH3)5](PR3)Cu in yields of 43% and 78%, respectively. A reaction between lithium pentamethylcyclopentadienide and copper(I) chloride in ethyl ether solution in the presence of carbon monoxide led to [η5-C5(CH3)5](CO)Cu. This carbonyl derivative was both air- and temperature-sensitive and decomposed in solution over 0 ºC to afford copper metal, carbon monoxide, and decamethyl-1,1′-dihydrofulvalene. A reaction between copper(I) chloride and bis(trimethylsilyl)acetylene produced [η2-(CH3)3SiC==CSi(CH3)3]2Cu2Cl2 in 76% yield. Treatment of the latter dimer with lithium pentamethylcyclopentadienide in ethyl ether solution afforded [η5-C5(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu. The parent compound (η5-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu was also obtained starting with lithium cyclopentadienide. Both products were air- and temperature-sensitive but could be readily converted into the respective triphenylphosphine derivatives. The complexes [η5-C5-(CH3)5][η2-(CH3)3SiC=CS í(CH3)3]Cu and (η2-C5H5)[η2-(CH3)3SiC=CSi(CH3)3]Cu represent the first “mixed-sandwich compounds of copper, as predicted by the effective atomic number (EAN) rule.

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U2 - 10.1021/ja00354a023

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SN - 0002-7863

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