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Bis(diphenylphosphino)methane dioxide complexes of lanthanide trichlorides: synthesis, structures and spectroscopy

Bis(diphenylphosphino)methane dioxide complexes of lanthanide trichlorides: synthesis, structures and spectroscopy
Bis(diphenylphosphino)methane dioxide complexes of lanthanide trichlorides: synthesis, structures and spectroscopy
Bis(diphenylphosphino)methane dioxide (dppmO2) forms eight-coordinate cations [M(dppmO2)4]Cl3 (M = La, Ce, Pr, Nd, Sm, Eu, Gd) on reaction in a 4:1 molar ratio with the appropriate LnCl3 in ethanol. Similar reaction in a 3:1 ratio produced seven-coordinate [M(dppmO2)3Cl]Cl2 (M = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), whilst LuCl3 alone produced six-coordinate [Lu(dppmO2)2Cl2]Cl. The complexes have been characterised by IR, 1H and 31P{1H}-NMR spectroscopy. X-ray structures show that [M(dppmO2)4]Cl3 (M = Ce, Sm, Gd) contain square antiprismatic cations, whilst [M(dppmO2)3Cl]Cl2 (M = Yb, Dy, Lu) have distorted pentagonal bipyramidal structures with apical Cl. The [Lu(dppmO2)2Cl2]Cl has a cis octahedral cation. The structure of [Yb(dppmO2)3(H2O)]Cl3-dppmO2 is also reported. The change in coordination numbers and geometry along the series is driven by the decreasing lanthanide cation radii, but the chloride counter anions also play a role.
lanthanide trichloride complexes, diphosphine dioxide, coordination complexes, x-ray structures
0712-4813
947-959
Bannister, Robert
87a8f77c-3e73-4b44-83aa-8885d77f6a99
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bannister, Robert
87a8f77c-3e73-4b44-83aa-8885d77f6a99
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Bannister, Robert, Levason, William and Reid, Gillian (2020) Bis(diphenylphosphino)methane dioxide complexes of lanthanide trichlorides: synthesis, structures and spectroscopy. Spectroscopy, 2 (4), 947-959. (doi:10.3390/chemistry2040060).

Record type: Article

Abstract

Bis(diphenylphosphino)methane dioxide (dppmO2) forms eight-coordinate cations [M(dppmO2)4]Cl3 (M = La, Ce, Pr, Nd, Sm, Eu, Gd) on reaction in a 4:1 molar ratio with the appropriate LnCl3 in ethanol. Similar reaction in a 3:1 ratio produced seven-coordinate [M(dppmO2)3Cl]Cl2 (M = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), whilst LuCl3 alone produced six-coordinate [Lu(dppmO2)2Cl2]Cl. The complexes have been characterised by IR, 1H and 31P{1H}-NMR spectroscopy. X-ray structures show that [M(dppmO2)4]Cl3 (M = Ce, Sm, Gd) contain square antiprismatic cations, whilst [M(dppmO2)3Cl]Cl2 (M = Yb, Dy, Lu) have distorted pentagonal bipyramidal structures with apical Cl. The [Lu(dppmO2)2Cl2]Cl has a cis octahedral cation. The structure of [Yb(dppmO2)3(H2O)]Cl3-dppmO2 is also reported. The change in coordination numbers and geometry along the series is driven by the decreasing lanthanide cation radii, but the chloride counter anions also play a role.

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More information

Accepted/In Press date: 16 November 2020
e-pub ahead of print date: 19 November 2020
Published date: December 2020
Keywords: lanthanide trichloride complexes, diphosphine dioxide, coordination complexes, x-ray structures

Identifiers

Local EPrints ID: 445236
URI: http://eprints.soton.ac.uk/id/eprint/445236
ISSN: 0712-4813
PURE UUID: 838b5b48-2ebb-49b8-937d-8ba54821c6de
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: 25 Nov 2020 17:33
Last modified: 18 Feb 2021 16:41

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