Experimental and theoretical investigation of Z-E alkene isomerization in [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) and related vinylalkylidenes

Xiang Niu, Lakshmi Gopal, Michael P. Masingale, Dale A. Braden, Bruce S Hudson, Michael Sponsler

Research output: Contribution to journalArticle

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Abstract

The conjugated dinithenium bisalkylidene complex [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) (1, an inseparable 10:1 mixture of E and Z alkene isomers 1E and 1Z) and the separate E and Z isomers of the monoruthenium alkylidene complexes (Cy3P)2Cl2Ru=CHCH=CHCH=CH2 (2E and 2Z) and (Cy3P)2Cl2Ru=CHCH=CHCH3 (3E and 3Z) have each been synthesized through the stoichiometric reaction of olefin metathesis catalysts. Each pair of isomers undergo Z-E isomerization, though the isomerization rates and their dependencies on excess alkene and PCy3 are very different. Isomerization in 1 is the fastest, with ΔH = 100 ± 5 kJ/mol and ΔS = 67 ± 3 J/(mol K) (1Z to 1E) or 49 ± 3 J/(mol K) (1E to 1Z) as determined by dynamic NMR, giving t1/2 = 11 s for the approach to equilibrium at 25°C. The rate of this isomerization shows no phosphine dependence. Isomerizations of 2Z and 3Z are slower (t1/2 = 5-20 h), but the former is promoted by PCy3, while the latter is inhibited. In the presence of (Z)-1,3,5-hexatriene, the isomerization of 2Z is much slower, while the isomerization of 3Z is accelerated by (Z)-1,3-pentadiene. Density functional calculations were performed to help interpret these results and elucidate which of several possible isomerization mechanisms operates in each case.

Original languageEnglish (US)
Pages (from-to)649-660
Number of pages12
JournalOrganometallics
Volume19
Issue number4
StatePublished - Feb 21 2000

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Alkenes
Isomerization
isomerization
alkenes
Isomers
phosphine
isomers
alkylidene
metathesis
phosphines
Density functional theory
Nuclear magnetic resonance
catalysts
nuclear magnetic resonance
Catalysts

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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Experimental and theoretical investigation of Z-E alkene isomerization in [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) and related vinylalkylidenes. / Niu, Xiang; Gopal, Lakshmi; Masingale, Michael P.; Braden, Dale A.; Hudson, Bruce S; Sponsler, Michael.

In: Organometallics, Vol. 19, No. 4, 21.02.2000, p. 649-660.

Research output: Contribution to journalArticle

Niu, Xiang ; Gopal, Lakshmi ; Masingale, Michael P. ; Braden, Dale A. ; Hudson, Bruce S ; Sponsler, Michael. / Experimental and theoretical investigation of Z-E alkene isomerization in [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) and related vinylalkylidenes. In: Organometallics. 2000 ; Vol. 19, No. 4. pp. 649-660.
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abstract = "The conjugated dinithenium bisalkylidene complex [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) (1, an inseparable 10:1 mixture of E and Z alkene isomers 1E and 1Z) and the separate E and Z isomers of the monoruthenium alkylidene complexes (Cy3P)2Cl2Ru=CHCH=CHCH=CH2 (2E and 2Z) and (Cy3P)2Cl2Ru=CHCH=CHCH3 (3E and 3Z) have each been synthesized through the stoichiometric reaction of olefin metathesis catalysts. Each pair of isomers undergo Z-E isomerization, though the isomerization rates and their dependencies on excess alkene and PCy3 are very different. Isomerization in 1 is the fastest, with ΔH‡ = 100 ± 5 kJ/mol and ΔS‡ = 67 ± 3 J/(mol K) (1Z to 1E) or 49 ± 3 J/(mol K) (1E to 1Z) as determined by dynamic NMR, giving t1/2 = 11 s for the approach to equilibrium at 25°C. The rate of this isomerization shows no phosphine dependence. Isomerizations of 2Z and 3Z are slower (t1/2 = 5-20 h), but the former is promoted by PCy3, while the latter is inhibited. In the presence of (Z)-1,3,5-hexatriene, the isomerization of 2Z is much slower, while the isomerization of 3Z is accelerated by (Z)-1,3-pentadiene. Density functional calculations were performed to help interpret these results and elucidate which of several possible isomerization mechanisms operates in each case.",
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N2 - The conjugated dinithenium bisalkylidene complex [(Cy3P)2Cl2Ru]2(μ-CHCH=CHCH) (1, an inseparable 10:1 mixture of E and Z alkene isomers 1E and 1Z) and the separate E and Z isomers of the monoruthenium alkylidene complexes (Cy3P)2Cl2Ru=CHCH=CHCH=CH2 (2E and 2Z) and (Cy3P)2Cl2Ru=CHCH=CHCH3 (3E and 3Z) have each been synthesized through the stoichiometric reaction of olefin metathesis catalysts. Each pair of isomers undergo Z-E isomerization, though the isomerization rates and their dependencies on excess alkene and PCy3 are very different. Isomerization in 1 is the fastest, with ΔH‡ = 100 ± 5 kJ/mol and ΔS‡ = 67 ± 3 J/(mol K) (1Z to 1E) or 49 ± 3 J/(mol K) (1E to 1Z) as determined by dynamic NMR, giving t1/2 = 11 s for the approach to equilibrium at 25°C. The rate of this isomerization shows no phosphine dependence. Isomerizations of 2Z and 3Z are slower (t1/2 = 5-20 h), but the former is promoted by PCy3, while the latter is inhibited. In the presence of (Z)-1,3,5-hexatriene, the isomerization of 2Z is much slower, while the isomerization of 3Z is accelerated by (Z)-1,3-pentadiene. Density functional calculations were performed to help interpret these results and elucidate which of several possible isomerization mechanisms operates in each case.

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