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Arsenic(III) halide complexes with phosphine and arsine co-ligands: synthesis, spectroscopic and structural properties

Arsenic(III) halide complexes with phosphine and arsine co-ligands: synthesis, spectroscopic and structural properties
Arsenic(III) halide complexes with phosphine and arsine co-ligands: synthesis, spectroscopic and structural properties
AsX3 (X = Cl, Br or I) reacts with one molar equivalent of L [L = o-C6H4(PMe2)(2), o-C6H4(PPh2)(2), o-C6H4(AsMe2)(2) or MeC(CH2AsMe2)(3)] in rigorously anhydrous CH2Cl2 or thf solution to give colourless or yellow solids of composition [AsX3L]. Using two molar equivalents of PMe3 with AsX3 affords solids of empirical formula [AsX3(PMe3)(2)], whereas one molar equivalent of PMe3 with AsCl3 gives the 1 : 1 complex [AsCl3(PMe3)]. Reaction of AsX3 with AsMe3 gives only the 1 : 1 product [AsX3(AsMe3)], whether using a 1 : 1 or 1 : 2 AsCl3 : AsMe3 ratio. The products have been characterised by microanalysis, and IR, H-1 NMR and P-31{H-1} NMR spectroscopies, where appropriate. The crystal structures of three species, [AsCl3(PMe3)], [AsBr3{o-C6H4(AsMe2)(2)}] and [AsI3{o-C6H4(AsMe2)(2)}] have been determined. [AsCl3(PMe3)] adopts a dimeric structure formed through mu-dichloro-bridged edge-shared square pyramidal moieties with anti PMe3 ligands in the axial sites. Interestingly, in the lattice, there are two crystallographically independent dimers which are arranged orthogonally with long range As ? ? ? Cl contacts between between them, giving rise to in finite chains. Thus, in one dimer the As centres are formally 5-coordinate, while in the adjacent dimer the coordination is [5 + 1]. The complexes [AsX3{o-C6H4(AsMe2)(2)}] (X = Br or I) are both dimeric through mu-dihalo-bridged bioctahedra in the isomer (A) form. Trends in bond length and angle distributions are considered and the stereochemical activity of the lone pair on the As(III) acceptor discussed.
crystal-structure, bismuth(iii)
1477-9226
1188-1192
Hill, Nicholas J.
c588ad7e-5668-46b9-b84a-791b664f37aa
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Hill, Nicholas J.
c588ad7e-5668-46b9-b84a-791b664f37aa
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Hill, Nicholas J., Levason, William and Reid, Gillian (2002) Arsenic(III) halide complexes with phosphine and arsine co-ligands: synthesis, spectroscopic and structural properties. Dalton Transactions, (6), 1188-1192. (doi:10.1039/b107926n).

Record type: Article

Abstract

AsX3 (X = Cl, Br or I) reacts with one molar equivalent of L [L = o-C6H4(PMe2)(2), o-C6H4(PPh2)(2), o-C6H4(AsMe2)(2) or MeC(CH2AsMe2)(3)] in rigorously anhydrous CH2Cl2 or thf solution to give colourless or yellow solids of composition [AsX3L]. Using two molar equivalents of PMe3 with AsX3 affords solids of empirical formula [AsX3(PMe3)(2)], whereas one molar equivalent of PMe3 with AsCl3 gives the 1 : 1 complex [AsCl3(PMe3)]. Reaction of AsX3 with AsMe3 gives only the 1 : 1 product [AsX3(AsMe3)], whether using a 1 : 1 or 1 : 2 AsCl3 : AsMe3 ratio. The products have been characterised by microanalysis, and IR, H-1 NMR and P-31{H-1} NMR spectroscopies, where appropriate. The crystal structures of three species, [AsCl3(PMe3)], [AsBr3{o-C6H4(AsMe2)(2)}] and [AsI3{o-C6H4(AsMe2)(2)}] have been determined. [AsCl3(PMe3)] adopts a dimeric structure formed through mu-dichloro-bridged edge-shared square pyramidal moieties with anti PMe3 ligands in the axial sites. Interestingly, in the lattice, there are two crystallographically independent dimers which are arranged orthogonally with long range As ? ? ? Cl contacts between between them, giving rise to in finite chains. Thus, in one dimer the As centres are formally 5-coordinate, while in the adjacent dimer the coordination is [5 + 1]. The complexes [AsX3{o-C6H4(AsMe2)(2)}] (X = Br or I) are both dimeric through mu-dihalo-bridged bioctahedra in the isomer (A) form. Trends in bond length and angle distributions are considered and the stereochemical activity of the lone pair on the As(III) acceptor discussed.

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More information

Published date: 2002
Keywords: crystal-structure, bismuth(iii)

Identifiers

Local EPrints ID: 19777
URI: http://eprints.soton.ac.uk/id/eprint/19777
ISSN: 1477-9226
PURE UUID: d7564ba5-fd08-4741-b0ce-33c6caa209e4
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 20 Feb 2006
Last modified: 09 Jan 2022 02:43

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Contributors

Author: Nicholas J. Hill
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD

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