A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts

Nicholas A. Barnes; Stephen M. Godfrey; Rana Z. Khan; Amber Pierce; Robin G. Pritchard

doi:10.1016/j.poly.2011.12.023

A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts

Nicholas A. Barnes, Stephen M. Godfrey, Rana Z. Khan, Amber Pierce, Robin G. Pritchard

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

Abstract

A series of Ar 3PI 2 adducts [Ar = (o-OCH 3C 6H 4), (m-OCH 3C 6H 4), (p-OCH 3C 6H 4), (o-SCH 3C 6H 4), (p-SCH 3C 6H 4), (m-FC 6H 4), (p-FC 6H 4), (p-ClC 6H 4)] have been synthesized via the 1:1 reactions of Ar 3P with di-iodine. The 31P{ 1H} NMR spectra of a series of Ar 3PI 2 adducts has been examined to resolve previous inconsistent reports. Ar 3PI 2 adducts do not ionize to [Ar 3PI]I in CDCl 3, and in many cases the molecular Ar 3PI 2 "spoke" adduct is stable in solution, with the degree of stability being highly dependent on the nature of the aryl group. The structures of the majority of these adducts have been established by X-ray diffraction studies. Whilst P-I and I-I bond lengths are primarily influenced by electronic effects, steric and crystal packing effects may also have an influence, as shown by the different polymorphs of (p-FC 6H 4) 3PI 2, where a change in the conformation of the aryl groups in one of the molecules results in a lengthening of the P-I bond and shortening of the I-I bond. © 2012 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	31-46
Number of pages	15
Journal	Polyhedron
Volume	35
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2011.12.023
Publication status	Published - 16 Mar 2012

Keywords

Charge transfer adducts
Crystal packing
Iodine
Ligand conformation
Phosphines

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10.1016/j.poly.2011.12.023

CCDC 843219: Experimental Crystal Structure Determination
Barnes, N. A. (Contributor), Godfrey, S. M. (Contributor), Khan, R. Z. (Contributor), Pierce, A. (Contributor) & Pritchard, R. (Contributor), Cambridge Crystallographic Data Centre, 2011
DOI: 10.5517/ccx9fm7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccx9fm7&sid=DataCite
Dataset
CCDC 843220: Experimental Crystal Structure Determination
Barnes, N. A. (Contributor), Godfrey, S. M. (Contributor), Khan, R. Z. (Contributor), Pierce, A. (Contributor) & Pritchard, R. (Contributor), Cambridge Crystallographic Data Centre, 2011
DOI: 10.5517/ccx9fn8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccx9fn8&sid=DataCite
Dataset
CCDC 843217: Experimental Crystal Structure Determination
Barnes, N. A. (Contributor), Godfrey, S. M. (Contributor), Khan, R. Z. (Contributor), Pierce, A. (Contributor) & Pritchard, R. (Contributor), Cambridge Crystallographic Data Centre, 2011
DOI: 10.5517/ccx9fk5, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccx9fk5&sid=DataCite
Dataset

Cite this

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title = "A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts",

abstract = "A series of Ar 3PI 2 adducts [Ar = (o-OCH 3C 6H 4), (m-OCH 3C 6H 4), (p-OCH 3C 6H 4), (o-SCH 3C 6H 4), (p-SCH 3C 6H 4), (m-FC 6H 4), (p-FC 6H 4), (p-ClC 6H 4)] have been synthesized via the 1:1 reactions of Ar 3P with di-iodine. The 31P{ 1H} NMR spectra of a series of Ar 3PI 2 adducts has been examined to resolve previous inconsistent reports. Ar 3PI 2 adducts do not ionize to [Ar 3PI]I in CDCl 3, and in many cases the molecular Ar 3PI 2 {"}spoke{"} adduct is stable in solution, with the degree of stability being highly dependent on the nature of the aryl group. The structures of the majority of these adducts have been established by X-ray diffraction studies. Whilst P-I and I-I bond lengths are primarily influenced by electronic effects, steric and crystal packing effects may also have an influence, as shown by the different polymorphs of (p-FC 6H 4) 3PI 2, where a change in the conformation of the aryl groups in one of the molecules results in a lengthening of the P-I bond and shortening of the I-I bond. {\textcopyright} 2012 Elsevier Ltd. All rights reserved.",

keywords = "Charge transfer adducts, Crystal packing, Iodine, Ligand conformation, Phosphines",

author = "Barnes, {Nicholas A.} and Godfrey, {Stephen M.} and Khan, {Rana Z.} and Amber Pierce and Pritchard, {Robin G.}",

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doi = "10.1016/j.poly.2011.12.023",

language = "English",

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pages = "31--46",

journal = "Polyhedron",

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T1 - A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts

AU - Barnes, Nicholas A.

AU - Godfrey, Stephen M.

AU - Khan, Rana Z.

AU - Pierce, Amber

AU - Pritchard, Robin G.

N1 - Times Cited: 1

PY - 2012/3/16

Y1 - 2012/3/16

N2 - A series of Ar 3PI 2 adducts [Ar = (o-OCH 3C 6H 4), (m-OCH 3C 6H 4), (p-OCH 3C 6H 4), (o-SCH 3C 6H 4), (p-SCH 3C 6H 4), (m-FC 6H 4), (p-FC 6H 4), (p-ClC 6H 4)] have been synthesized via the 1:1 reactions of Ar 3P with di-iodine. The 31P{ 1H} NMR spectra of a series of Ar 3PI 2 adducts has been examined to resolve previous inconsistent reports. Ar 3PI 2 adducts do not ionize to [Ar 3PI]I in CDCl 3, and in many cases the molecular Ar 3PI 2 "spoke" adduct is stable in solution, with the degree of stability being highly dependent on the nature of the aryl group. The structures of the majority of these adducts have been established by X-ray diffraction studies. Whilst P-I and I-I bond lengths are primarily influenced by electronic effects, steric and crystal packing effects may also have an influence, as shown by the different polymorphs of (p-FC 6H 4) 3PI 2, where a change in the conformation of the aryl groups in one of the molecules results in a lengthening of the P-I bond and shortening of the I-I bond. © 2012 Elsevier Ltd. All rights reserved.

AB - A series of Ar 3PI 2 adducts [Ar = (o-OCH 3C 6H 4), (m-OCH 3C 6H 4), (p-OCH 3C 6H 4), (o-SCH 3C 6H 4), (p-SCH 3C 6H 4), (m-FC 6H 4), (p-FC 6H 4), (p-ClC 6H 4)] have been synthesized via the 1:1 reactions of Ar 3P with di-iodine. The 31P{ 1H} NMR spectra of a series of Ar 3PI 2 adducts has been examined to resolve previous inconsistent reports. Ar 3PI 2 adducts do not ionize to [Ar 3PI]I in CDCl 3, and in many cases the molecular Ar 3PI 2 "spoke" adduct is stable in solution, with the degree of stability being highly dependent on the nature of the aryl group. The structures of the majority of these adducts have been established by X-ray diffraction studies. Whilst P-I and I-I bond lengths are primarily influenced by electronic effects, steric and crystal packing effects may also have an influence, as shown by the different polymorphs of (p-FC 6H 4) 3PI 2, where a change in the conformation of the aryl groups in one of the molecules results in a lengthening of the P-I bond and shortening of the I-I bond. © 2012 Elsevier Ltd. All rights reserved.

KW - Charge transfer adducts

KW - Crystal packing

KW - Iodine

KW - Ligand conformation

KW - Phosphines

U2 - 10.1016/j.poly.2011.12.023

DO - 10.1016/j.poly.2011.12.023

M3 - Article

SN - 0277-5387

VL - 35

SP - 31

EP - 46

JO - Polyhedron

JF - Polyhedron

IS - 1

ER -

A structural and spectroscopic study of tris-aryl substituted R 3PI 2 adducts

Abstract

Keywords

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Datasets

CCDC 843219: Experimental Crystal Structure Determination

CCDC 843220: Experimental Crystal Structure Determination

CCDC 843217: Experimental Crystal Structure Determination

Cite this