C-O and C-S bond cleavage in chelating diethers and thioethers promoted by η9,η5-bis(indenyl)zirconium sandwich complexes: A combined experimental and computational study

Christopher A. Bradley; Luis F. Veiros; Paul J. Chirik

doi:10.1021/om0701120

C-O and C-S bond cleavage in chelating diethers and thioethers promoted by η⁹,η⁵-bis(indenyl)zirconium sandwich complexes: A combined experimental and computational study

Christopher A. Bradley, Luis F. Veiros, Paul J. Chirik

Research output: Contribution to journal › Article › peer-review

43 Scopus citations

Abstract

Gently warming the η⁶,η⁵-bis(indenyl) zirconium dimethoxyethane compound (η⁶-C₉H ₅-1,3-(SiMe₃)₂)-(η⁵-C ₉H₅-1,3-(SiMe₃)₂)Zr(DME) (1-DME) to 45°C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (η⁵-C₉H ₅-1,3-(SiMe₃)₂)₂Zr(η ²-CH₂=CH²) and the corresponding zirconium bis(methoxide) complex (η⁵-C₉H₅-1,3- (SiMe₃)₂)₂Zr(OMe)₂. Monitoring the relative rates of 1-DME versus 1-DME-d₁₀ cleavage by ¹H NMR spectroscopy established no kinetic isotope effect (k_H/k _D = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the η⁶, η⁵-bis(indenyl)zirconium complex followed by facile η⁶ to η⁵ indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.

Original language	English (US)
Pages (from-to)	3191-3200
Number of pages	10
Journal	Organometallics
Volume	26
Issue number	13
DOIs	https://doi.org/10.1021/om0701120
State	Published - Jun 18 2007
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om0701120

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@article{e70ae188d99a4d4bbbdfa6d5a167b8ee,

title = "C-O and C-S bond cleavage in chelating diethers and thioethers promoted by η9,η5-bis(indenyl)zirconium sandwich complexes: A combined experimental and computational study",

abstract = "Gently warming the η6,η5-bis(indenyl) zirconium dimethoxyethane compound (η6-C9H 5-1,3-(SiMe3)2)-(η5-C 9H5-1,3-(SiMe3)2)Zr(DME) (1-DME) to 45°C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (η5-C9H 5-1,3-(SiMe3)2)2Zr(η 2-CH2=CH2) and the corresponding zirconium bis(methoxide) complex (η5-C9H5-1,3- (SiMe3)2)2Zr(OMe)2. Monitoring the relative rates of 1-DME versus 1-DME-d10 cleavage by 1H NMR spectroscopy established no kinetic isotope effect (kH/k D = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the η6, η5-bis(indenyl)zirconium complex followed by facile η6 to η5 indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.",

author = "Bradley, {Christopher A.} and Veiros, {Luis F.} and Chirik, {Paul J.}",

year = "2007",

month = jun,

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doi = "10.1021/om0701120",

language = "English (US)",

volume = "26",

pages = "3191--3200",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - C-O and C-S bond cleavage in chelating diethers and thioethers promoted by η9,η5-bis(indenyl)zirconium sandwich complexes

T2 - A combined experimental and computational study

AU - Bradley, Christopher A.

AU - Veiros, Luis F.

AU - Chirik, Paul J.

PY - 2007/6/18

Y1 - 2007/6/18

N2 - Gently warming the η6,η5-bis(indenyl) zirconium dimethoxyethane compound (η6-C9H 5-1,3-(SiMe3)2)-(η5-C 9H5-1,3-(SiMe3)2)Zr(DME) (1-DME) to 45°C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (η5-C9H 5-1,3-(SiMe3)2)2Zr(η 2-CH2=CH2) and the corresponding zirconium bis(methoxide) complex (η5-C9H5-1,3- (SiMe3)2)2Zr(OMe)2. Monitoring the relative rates of 1-DME versus 1-DME-d10 cleavage by 1H NMR spectroscopy established no kinetic isotope effect (kH/k D = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the η6, η5-bis(indenyl)zirconium complex followed by facile η6 to η5 indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.

AB - Gently warming the η6,η5-bis(indenyl) zirconium dimethoxyethane compound (η6-C9H 5-1,3-(SiMe3)2)-(η5-C 9H5-1,3-(SiMe3)2)Zr(DME) (1-DME) to 45°C resulted in C-O bond scission to yield an equimolar mixture of the zirconocene ethylene compound (η5-C9H 5-1,3-(SiMe3)2)2Zr(η 2-CH2=CH2) and the corresponding zirconium bis(methoxide) complex (η5-C9H5-1,3- (SiMe3)2)2Zr(OMe)2. Monitoring the relative rates of 1-DME versus 1-DME-d10 cleavage by 1H NMR spectroscopy established no kinetic isotope effect (kH/k D = 1.0(1)), eliminating the possibility of C-H activation in or prior to the rate-determining step. Computational studies support a pathway involving rate-determining DME dissociation from the η6, η5-bis(indenyl)zirconium complex followed by facile η6 to η5 indenyl haptotropic rearrangement and C-O bond scission. Corresponding C-S bond cleavage chemistry has been investigated for three thioethers and the mechanism of bond activation compared to the oxygen congeners.

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ER -

C-O and C-S bond cleavage in chelating diethers and thioethers promoted by η⁹,η⁵-bis(indenyl)zirconium sandwich complexes: A combined experimental and computational study

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