The synthesis and characterization of four new uranium(IV) chlorophosphates: UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3)

Matthew D. Ward; Ian Y. Chan; Sébastien Lebègue; James A. Ibers

doi:10.1021/ic501781h

The synthesis and characterization of four new uranium(IV) chlorophosphates: UCl₄(POCl₃), [U₂Cl₉][PCl₄], UCl₃(PO₂Cl₂), and U₂Cl₈(POCl₃)

Matthew D. Ward, Ian Y. Chan, Sébastien Lebègue, James A. Ibers^*

^*Corresponding author for this work

Chemistry

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

Abstract

The new uranium(IV) chlorophosphate compounds UCl₄(POCl₃) and [U₂Cl₉][PCl₄] have been synthesized by the solid-state reactions of U, P₂O₅, and PCl₅ at 648 K; the compounds UCl₃(PO₂Cl₂) and U₂Cl₈(POCl₃) have been synthesized at 648 K with the same reactants plus added S. Their structures are, respectively, chainlike, a simple salt, three-dimensional, and sheetlike. From abinitio calculations, U₂Cl₈(POCl₃) and UCl₃(PO₂Cl₂) are found to be ferromagnetic, whereas UCl₄(POCl₃) is found to be antiferromagnetic. U₂Cl₈(POCl₃) is a strong metal, whereas UCl₃(PO₂Cl₂) is a weaker metal. In contrast, UCl₄(POCl₃) has a finite band gap, with a value of 0.35 eV.

Original language	English (US)
Pages (from-to)	9969-9975
Number of pages	7
Journal	Inorganic chemistry
Volume	53
Issue number	18
DOIs	https://doi.org/10.1021/ic501781h
State	Published - Sep 15 2014

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic501781h

Cite this

@article{58a19bbc441446f69206b6bc32d0dabc,

title = "The synthesis and characterization of four new uranium(IV) chlorophosphates: UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3)",

abstract = "The new uranium(IV) chlorophosphate compounds UCl4(POCl3) and [U2Cl9][PCl4] have been synthesized by the solid-state reactions of U, P2O5, and PCl5 at 648 K; the compounds UCl3(PO2Cl2) and U2Cl8(POCl3) have been synthesized at 648 K with the same reactants plus added S. Their structures are, respectively, chainlike, a simple salt, three-dimensional, and sheetlike. From abinitio calculations, U2Cl8(POCl3) and UCl3(PO2Cl2) are found to be ferromagnetic, whereas UCl4(POCl3) is found to be antiferromagnetic. U2Cl8(POCl3) is a strong metal, whereas UCl3(PO2Cl2) is a weaker metal. In contrast, UCl4(POCl3) has a finite band gap, with a value of 0.35 eV.",

author = "Ward, {Matthew D.} and Chan, {Ian Y.} and S{\'e}bastien Leb{\`e}gue and Ibers, {James A.}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = sep,

day = "15",

doi = "10.1021/ic501781h",

language = "English (US)",

volume = "53",

pages = "9969--9975",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "18",

}

TY - JOUR

T1 - The synthesis and characterization of four new uranium(IV) chlorophosphates

T2 - UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3)

AU - Ward, Matthew D.

AU - Chan, Ian Y.

AU - Lebègue, Sébastien

AU - Ibers, James A.

PY - 2014/9/15

Y1 - 2014/9/15

N2 - The new uranium(IV) chlorophosphate compounds UCl4(POCl3) and [U2Cl9][PCl4] have been synthesized by the solid-state reactions of U, P2O5, and PCl5 at 648 K; the compounds UCl3(PO2Cl2) and U2Cl8(POCl3) have been synthesized at 648 K with the same reactants plus added S. Their structures are, respectively, chainlike, a simple salt, three-dimensional, and sheetlike. From abinitio calculations, U2Cl8(POCl3) and UCl3(PO2Cl2) are found to be ferromagnetic, whereas UCl4(POCl3) is found to be antiferromagnetic. U2Cl8(POCl3) is a strong metal, whereas UCl3(PO2Cl2) is a weaker metal. In contrast, UCl4(POCl3) has a finite band gap, with a value of 0.35 eV.

AB - The new uranium(IV) chlorophosphate compounds UCl4(POCl3) and [U2Cl9][PCl4] have been synthesized by the solid-state reactions of U, P2O5, and PCl5 at 648 K; the compounds UCl3(PO2Cl2) and U2Cl8(POCl3) have been synthesized at 648 K with the same reactants plus added S. Their structures are, respectively, chainlike, a simple salt, three-dimensional, and sheetlike. From abinitio calculations, U2Cl8(POCl3) and UCl3(PO2Cl2) are found to be ferromagnetic, whereas UCl4(POCl3) is found to be antiferromagnetic. U2Cl8(POCl3) is a strong metal, whereas UCl3(PO2Cl2) is a weaker metal. In contrast, UCl4(POCl3) has a finite band gap, with a value of 0.35 eV.

UR - http://www.scopus.com/inward/record.url?scp=84919711832&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84919711832&partnerID=8YFLogxK

U2 - 10.1021/ic501781h

DO - 10.1021/ic501781h

M3 - Article

C2 - 25166304

AN - SCOPUS:84919711832

SN - 0020-1669

VL - 53

SP - 9969

EP - 9975

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 18

ER -

The synthesis and characterization of four new uranium(IV) chlorophosphates: UCl₄(POCl₃), [U₂Cl₉][PCl₄], UCl₃(PO₂Cl₂), and U₂Cl₈(POCl₃)

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this