BONDING IN YXXY DIHALIDES AND DIHYDRIDES OF DIOXYGEN AND DISULFUR

D R  ALLERES; D L  COOPER; T P  CUNNINGHAM; J  GERRATT; P B  KARADAKOV; M  RAIMONDI

BONDING IN YXXY DIHALIDES AND DIHYDRIDES OF DIOXYGEN AND DISULFUR

D R ALLERES, D L COOPER, T P CUNNINGHAM, J GERRATT, P B KARADAKOV, M RAIMONDI

Chemistry

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

Abstract

Ab initio calculations based on spin-coupled theory are used to compare and contrast the bonding in FOOF, HOOH, FSSF, CISSCI and HSSH, with emphasis on rationalising the striking variations in bond length. The resulting modern VB descriptions of the X-Y sigma-like bonds closely parallel those for the analogous XY(2) species, except for the expected changes to the orbital overlaps induced by the different bond lengths. In examining the variations in geometry, it seems that the most relevant aspect of, the bonding is that provided by the various p(pi)-like orbitals. In FOOF, FSSF and, to a lesser extent, CISSCI, incipient hypercoordinate character is observed (at oxygen or sulfur), with two partial pi-like interactions in approximately perpendicular planes, as well as some antibonding character in the X-Y bonds.

Original language	English
Pages (from-to)	3357-3362
Number of pages	6
Journal	JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
Volume	91
Issue number	19
Publication status	Published - 7 Oct 1995

Keywords

VALENCE

Cite this

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title = "BONDING IN YXXY DIHALIDES AND DIHYDRIDES OF DIOXYGEN AND DISULFUR",

abstract = "Ab initio calculations based on spin-coupled theory are used to compare and contrast the bonding in FOOF, HOOH, FSSF, CISSCI and HSSH, with emphasis on rationalising the striking variations in bond length. The resulting modern VB descriptions of the X-Y sigma-like bonds closely parallel those for the analogous XY(2) species, except for the expected changes to the orbital overlaps induced by the different bond lengths. In examining the variations in geometry, it seems that the most relevant aspect of, the bonding is that provided by the various p(pi)-like orbitals. In FOOF, FSSF and, to a lesser extent, CISSCI, incipient hypercoordinate character is observed (at oxygen or sulfur), with two partial pi-like interactions in approximately perpendicular planes, as well as some antibonding character in the X-Y bonds.",

keywords = "VALENCE",

author = "ALLERES, {D R} and COOPER, {D L} and CUNNINGHAM, {T P} and J GERRATT and KARADAKOV, {P B} and M RAIMONDI",

year = "1995",

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T1 - BONDING IN YXXY DIHALIDES AND DIHYDRIDES OF DIOXYGEN AND DISULFUR

AU - ALLERES, D R

AU - COOPER, D L

AU - CUNNINGHAM, T P

AU - GERRATT, J

AU - KARADAKOV, P B

AU - RAIMONDI, M

PY - 1995/10/7

Y1 - 1995/10/7

N2 - Ab initio calculations based on spin-coupled theory are used to compare and contrast the bonding in FOOF, HOOH, FSSF, CISSCI and HSSH, with emphasis on rationalising the striking variations in bond length. The resulting modern VB descriptions of the X-Y sigma-like bonds closely parallel those for the analogous XY(2) species, except for the expected changes to the orbital overlaps induced by the different bond lengths. In examining the variations in geometry, it seems that the most relevant aspect of, the bonding is that provided by the various p(pi)-like orbitals. In FOOF, FSSF and, to a lesser extent, CISSCI, incipient hypercoordinate character is observed (at oxygen or sulfur), with two partial pi-like interactions in approximately perpendicular planes, as well as some antibonding character in the X-Y bonds.

AB - Ab initio calculations based on spin-coupled theory are used to compare and contrast the bonding in FOOF, HOOH, FSSF, CISSCI and HSSH, with emphasis on rationalising the striking variations in bond length. The resulting modern VB descriptions of the X-Y sigma-like bonds closely parallel those for the analogous XY(2) species, except for the expected changes to the orbital overlaps induced by the different bond lengths. In examining the variations in geometry, it seems that the most relevant aspect of, the bonding is that provided by the various p(pi)-like orbitals. In FOOF, FSSF and, to a lesser extent, CISSCI, incipient hypercoordinate character is observed (at oxygen or sulfur), with two partial pi-like interactions in approximately perpendicular planes, as well as some antibonding character in the X-Y bonds.

KW - VALENCE

M3 - Article

SN - 0956-5000

VL - 91

SP - 3357

EP - 3362

JO - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

JF - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

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