CATALYTIC CHEMISTRY OF FURAN AND THIOPHENE - AB-INITIO CALCULATIONS, USING THE SPIN-COUPLED VALENCE-BOND METHOD, OF THE INTERACTION OF FURAN AND THIOPHENE WITH A POSITIVELY CHARGED CENTER

P C H  MITCHELL; G M  RAOS; P B  KARADAKOV; J  GERRATT; D L  COOPER

CATALYTIC CHEMISTRY OF FURAN AND THIOPHENE - AB-INITIO CALCULATIONS, USING THE SPIN-COUPLED VALENCE-BOND METHOD, OF THE INTERACTION OF FURAN AND THIOPHENE WITH A POSITIVELY CHARGED CENTER

P C H MITCHELL, G M RAOS, P B KARADAKOV, J GERRATT, D L COOPER

Chemistry

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

Abstract

The spin-coupled valence bond (SC-VB) method is summarized and used to determine the electronic structure of furan and thiophene. The resulting wavefunctions are utilized in a study of the interaction of these molecules with an approaching Li+ ion. It is found that the SC-VB description of the lone pairs of the heteroatoms provides a coherent explanation of the unusual fact that, in the minimum-energy structure of the thiophene-Li+ complex, the Li+ ion lies off the C-2 axis (at an angle of 50 degrees), whereas for the furan complex the Li+ ion lies on the C-2 axis. It is suggested that the interactions are sufficient to constrain the molecules at a positive centre on the surface of a catalyst without developing such strong bonds that the catalyst would be poisoned. The implications of this description for the catalytic activation of thiophene by transition-metal ions are discussed.

Original language	English
Pages (from-to)	749-758
Number of pages	10
Journal	JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
Volume	91
Issue number	4
Publication status	Published - 21 Feb 1995

Keywords

MOLYBDENUM-DISULFIDE CATALYST
MOLECULAR MECHANICS
WAVE-FUNCTION
HYDRODESULFURIZATION
COMPLEXES
CHEMISORPTION
COORDINATION
SULFUR
MODEL
MOS2

Cite this

@article{36db151f2283420ea95fa4828a19f1d7,

title = "CATALYTIC CHEMISTRY OF FURAN AND THIOPHENE - AB-INITIO CALCULATIONS, USING THE SPIN-COUPLED VALENCE-BOND METHOD, OF THE INTERACTION OF FURAN AND THIOPHENE WITH A POSITIVELY CHARGED CENTER",

abstract = "The spin-coupled valence bond (SC-VB) method is summarized and used to determine the electronic structure of furan and thiophene. The resulting wavefunctions are utilized in a study of the interaction of these molecules with an approaching Li+ ion. It is found that the SC-VB description of the lone pairs of the heteroatoms provides a coherent explanation of the unusual fact that, in the minimum-energy structure of the thiophene-Li+ complex, the Li+ ion lies off the C-2 axis (at an angle of 50 degrees), whereas for the furan complex the Li+ ion lies on the C-2 axis. It is suggested that the interactions are sufficient to constrain the molecules at a positive centre on the surface of a catalyst without developing such strong bonds that the catalyst would be poisoned. The implications of this description for the catalytic activation of thiophene by transition-metal ions are discussed.",

keywords = "MOLYBDENUM-DISULFIDE CATALYST, MOLECULAR MECHANICS, WAVE-FUNCTION, HYDRODESULFURIZATION, COMPLEXES, CHEMISORPTION, COORDINATION, SULFUR, MODEL, MOS2",

author = "MITCHELL, {P C H} and RAOS, {G M} and KARADAKOV, {P B} and J GERRATT and COOPER, {D L}",

year = "1995",

month = feb,

day = "21",

language = "English",

volume = "91",

pages = "749--758",

journal = "JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS",

issn = "0956-5000",

publisher = "The Royal Society of Chemistry",

number = "4",

}

CATALYTIC CHEMISTRY OF FURAN AND THIOPHENE - AB-INITIO CALCULATIONS, USING THE SPIN-COUPLED VALENCE-BOND METHOD, OF THE INTERACTION OF FURAN AND THIOPHENE WITH A POSITIVELY CHARGED CENTER. / MITCHELL, P C H ; RAOS, G M ; KARADAKOV, P B et al.
In: JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, Vol. 91, No. 4, 21.02.1995, p. 749-758.

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

TY - JOUR

T1 - CATALYTIC CHEMISTRY OF FURAN AND THIOPHENE - AB-INITIO CALCULATIONS, USING THE SPIN-COUPLED VALENCE-BOND METHOD, OF THE INTERACTION OF FURAN AND THIOPHENE WITH A POSITIVELY CHARGED CENTER

AU - MITCHELL, P C H

AU - RAOS, G M

AU - KARADAKOV, P B

AU - GERRATT, J

AU - COOPER, D L

PY - 1995/2/21

Y1 - 1995/2/21

N2 - The spin-coupled valence bond (SC-VB) method is summarized and used to determine the electronic structure of furan and thiophene. The resulting wavefunctions are utilized in a study of the interaction of these molecules with an approaching Li+ ion. It is found that the SC-VB description of the lone pairs of the heteroatoms provides a coherent explanation of the unusual fact that, in the minimum-energy structure of the thiophene-Li+ complex, the Li+ ion lies off the C-2 axis (at an angle of 50 degrees), whereas for the furan complex the Li+ ion lies on the C-2 axis. It is suggested that the interactions are sufficient to constrain the molecules at a positive centre on the surface of a catalyst without developing such strong bonds that the catalyst would be poisoned. The implications of this description for the catalytic activation of thiophene by transition-metal ions are discussed.

AB - The spin-coupled valence bond (SC-VB) method is summarized and used to determine the electronic structure of furan and thiophene. The resulting wavefunctions are utilized in a study of the interaction of these molecules with an approaching Li+ ion. It is found that the SC-VB description of the lone pairs of the heteroatoms provides a coherent explanation of the unusual fact that, in the minimum-energy structure of the thiophene-Li+ complex, the Li+ ion lies off the C-2 axis (at an angle of 50 degrees), whereas for the furan complex the Li+ ion lies on the C-2 axis. It is suggested that the interactions are sufficient to constrain the molecules at a positive centre on the surface of a catalyst without developing such strong bonds that the catalyst would be poisoned. The implications of this description for the catalytic activation of thiophene by transition-metal ions are discussed.

KW - MOLYBDENUM-DISULFIDE CATALYST

KW - MOLECULAR MECHANICS

KW - WAVE-FUNCTION

KW - HYDRODESULFURIZATION

KW - COMPLEXES

KW - CHEMISORPTION

KW - COORDINATION

KW - SULFUR

KW - MODEL

KW - MOS2

M3 - Article

SN - 0956-5000

VL - 91

SP - 749

EP - 758

JO - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

JF - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

IS - 4

ER -