Unusual chalcogen-boron ring compounds: the gas-phase structures of 1,4-B4S2(NMe2)4 and related molecules

Derek A. Wann; Heather E. Robertson; George Bramham; Andrew E. A. Bull; Nicholas C. Norman; Christopher A. Russell; David W. H. Rankin

doi:10.1039/b817410e

Unusual chalcogen-boron ring compounds: the gas-phase structures of 1,4-B₄S₂(NMe₂)₄ and related molecules

Derek A. Wann, Heather E. Robertson, George Bramham, Andrew E. A. Bull, Nicholas C. Norman, Christopher A. Russell, David W. H. Rankin

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

Abstract / Description of output

The structure of 1,4-B₄S₂(NMe₂)₄ has been determined by gas-phase electron diffraction and quantum chemical calculations and is compared with the known solid-state structure. While these structures are similar, with a twisted ring geometry [the dihedral angle S-B-B-S from electron diffraction is 75.4(16)°], they are strikingly different to the solid-state structure of 1,4-B₄O₂(OH)₄, which is planar. Using quantum chemical calculations, the combinations of O or S in the ring and OH or NMe₂ as the substituent have been studied and it has been shown that there are two separate causes of the twisted ring. Since the calculated (and observed) structure of 1,4-B₄O₂(OH)₄ is planar but that of 1,4-B₄S₂(OH)₄ is twisted, it is concluded that the inclusion of sulfur in the ring twists the structure by approximately 40°. By comparing the structures of 1,4-B₄S₂(OH)₄ and 1,4-B₄S₂(NMe₂)₄ it has been determined that the twist caused by the NMe₂ groups is around 30°.

Original language	English
Pages (from-to)	1446-1449
Number of pages	4
Journal	Dalton Transactions
Issue number	8
DOIs	https://doi.org/10.1039/b817410e
Publication status	Published - 2009

Keywords / Materials (for Non-textual outputs)

VALENCE BASIS-SETS
ORBITAL METHODS
ELECTRON-DIFFRACTION
CRYSTALLINE PHASES
2ND-ROW ELEMENTS
AB-INITIO
CHEMISTRY
SYSTEMS

Access to Document

10.1039/b817410e

Unusual chalcogen-boron ring compounds: the gas-phase structures of 1,4-B4S2(NMe2)4 and related moleculesFinal published version, 121 KB

http://pubs.rsc.org/en/Content/ArticleLanding/2009/DT/b817410e

Cite this

@article{4053b9200bc541409a72b2e0d99e309e,

title = "Unusual chalcogen-boron ring compounds: the gas-phase structures of 1,4-B4S2(NMe2)4 and related molecules",

abstract = "The structure of 1,4-B4S2(NMe2)4 has been determined by gas-phase electron diffraction and quantum chemical calculations and is compared with the known solid-state structure. While these structures are similar, with a twisted ring geometry [the dihedral angle S-B-B-S from electron diffraction is 75.4(16)°], they are strikingly different to the solid-state structure of 1,4-B4O2(OH)4, which is planar. Using quantum chemical calculations, the combinations of O or S in the ring and OH or NMe2 as the substituent have been studied and it has been shown that there are two separate causes of the twisted ring. Since the calculated (and observed) structure of 1,4-B4O2(OH)4 is planar but that of 1,4-B4S2(OH)4 is twisted, it is concluded that the inclusion of sulfur in the ring twists the structure by approximately 40°. By comparing the structures of 1,4-B4S2(OH)4 and 1,4-B4S2(NMe2)4 it has been determined that the twist caused by the NMe2 groups is around 30°.",

keywords = "VALENCE BASIS-SETS, ORBITAL METHODS, ELECTRON-DIFFRACTION, CRYSTALLINE PHASES, 2ND-ROW ELEMENTS, AB-INITIO, CHEMISTRY, SYSTEMS",

author = "Wann, {Derek A.} and Robertson, {Heather E.} and George Bramham and Bull, {Andrew E. A.} and Norman, {Nicholas C.} and Russell, {Christopher A.} and Rankin, {David W. H.}",

year = "2009",

doi = "10.1039/b817410e",

language = "English",

pages = "1446--1449",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Unusual chalcogen-boron ring compounds: the gas-phase structures of 1,4-B4S2(NMe2)4 and related molecules

AU - Wann, Derek A.

AU - Robertson, Heather E.

AU - Bramham, George

AU - Bull, Andrew E. A.

AU - Norman, Nicholas C.

AU - Russell, Christopher A.

AU - Rankin, David W. H.

PY - 2009

Y1 - 2009

N2 - The structure of 1,4-B4S2(NMe2)4 has been determined by gas-phase electron diffraction and quantum chemical calculations and is compared with the known solid-state structure. While these structures are similar, with a twisted ring geometry [the dihedral angle S-B-B-S from electron diffraction is 75.4(16)°], they are strikingly different to the solid-state structure of 1,4-B4O2(OH)4, which is planar. Using quantum chemical calculations, the combinations of O or S in the ring and OH or NMe2 as the substituent have been studied and it has been shown that there are two separate causes of the twisted ring. Since the calculated (and observed) structure of 1,4-B4O2(OH)4 is planar but that of 1,4-B4S2(OH)4 is twisted, it is concluded that the inclusion of sulfur in the ring twists the structure by approximately 40°. By comparing the structures of 1,4-B4S2(OH)4 and 1,4-B4S2(NMe2)4 it has been determined that the twist caused by the NMe2 groups is around 30°.

AB - The structure of 1,4-B4S2(NMe2)4 has been determined by gas-phase electron diffraction and quantum chemical calculations and is compared with the known solid-state structure. While these structures are similar, with a twisted ring geometry [the dihedral angle S-B-B-S from electron diffraction is 75.4(16)°], they are strikingly different to the solid-state structure of 1,4-B4O2(OH)4, which is planar. Using quantum chemical calculations, the combinations of O or S in the ring and OH or NMe2 as the substituent have been studied and it has been shown that there are two separate causes of the twisted ring. Since the calculated (and observed) structure of 1,4-B4O2(OH)4 is planar but that of 1,4-B4S2(OH)4 is twisted, it is concluded that the inclusion of sulfur in the ring twists the structure by approximately 40°. By comparing the structures of 1,4-B4S2(OH)4 and 1,4-B4S2(NMe2)4 it has been determined that the twist caused by the NMe2 groups is around 30°.

KW - VALENCE BASIS-SETS

KW - ORBITAL METHODS

KW - ELECTRON-DIFFRACTION

KW - CRYSTALLINE PHASES

KW - 2ND-ROW ELEMENTS

KW - AB-INITIO

KW - CHEMISTRY

KW - SYSTEMS

U2 - 10.1039/b817410e

DO - 10.1039/b817410e

M3 - Article

SN - 1477-9226

SP - 1446

EP - 1449

JO - Dalton Transactions

JF - Dalton Transactions

IS - 8

ER -