The University of Southampton
University of Southampton Institutional Repository
Warning ePrints Soton is experiencing an issue with some file downloads not being available. We are working hard to fix this. Please bear with us.

Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study

Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study
Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study
The uranyl(VI) ‘Pacman’ complex [(UO2)(py)(H2L)] A (L = polypyrrolic Schiff-base macrocycle) is reduced by Cp2Ti(η2-Me3SiC[triple bond, length as m-dash]CSiMe3) and [Cp2TiCl]2 to oxo-titanated uranyl(V) complexes [(py)(Cp2TiIIIOUO)(py)(H2L)] 1 and [(ClCp2TiIVOUO)(py)(H2L)] 2. Combination of ZrII and ZrIV synthons with A yields the first ZrIV–uranyl(V) complex, [(ClCp2ZrOUO)(py)(H2L)] 3. Similarly, combinations of Ae0 and AeII synthons (Ae = alkaline earth) afford the mono-oxo metalated uranyl(V) complexes [(py)2(ClMgOUO)(py)(H2L)] 4, [(py)2(thf)2(ICaOUO)(py) (H2L)] 5; the zinc complexes [(py)2(XZnOUO)(py)(H2L)] (X = Cl 6, I 7) are formed in a similar manner. In contrast, the direct reactions of Rb or Cs metal with A generate the first mono-rubidiated and mono-caesiated uranyl(V) complexes; monomeric [(py)3(RbOUO)(py)(H2L)] 8 and hexameric [(MOUO)(py)(H2L)]6 (M = Rb 8b or Cs 9). In these uranyl(V) complexes, the pyrrole N–H atoms show strengthened hydrogen-bonding interactions with the endo-oxos, classified computationally as moderate-strength hydrogen bonds. Computational DFT MO (density functional theory molecular orbital) and EDA (energy decomposition analysis), uranium M4 edge HR-XANES (High Energy Resolution X-ray Absorption Near Edge Structure) and 3d4f RIXS (Resonant Inelastic X-ray Scattering) have been used (the latter two for the first time for uranyl(V) in 7 (ZnI)) to compare the covalent character in the UV–O and O–M bonds and show the 5f orbitals in uranyl(VI) complex A are unexpectedly more delocalised than in the uranyl(V) 7 (ZnI) complex. The Oexo–Zn bonds have a larger covalent contribution compared to the Mg–Oexo/Ca–Oexo bonds, and more covalency is found in the U–Oexo bond in 7 (ZnI), in agreement with the calculations.
2041-6520
9740-9751
Zegke, Markus
d5b0b2dd-4018-4fc2-8b31-dbbdefb67ca1
Zhang, Xiaobin
250668b7-bb5d-41a8-8f04-414d4d575a06
Pidchenko, Ivan
948b815c-a3cf-4fae-9d9e-3580f6b60e3c
Hlina, Johann A.
00eb0494-2f0a-4ddb-9724-6ac27954ebcf
Lord, Rianne M.
0aeaa411-8ad5-43f5-a73f-3b42cefd864b
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Nichol, Gary S.
016249ad-f036-477d-9f6e-dd1bc619e372
Magnani, Nicola
39ba7df4-715a-4992-a1f2-052df5bac72e
Schreckenbach, Georg
c7d93e35-34e0-4c57-870d-9a051a85271d
Vitova, Tonya
06bcae55-d7b4-45be-9ea8-7e3f4368309f
Love, Jason B.
86349ecb-c5c7-4151-bd43-d79ddd214b27
Arnold, Polly L.
431d494e-712d-4677-9ee2-0bcefe8a5ca0
Zegke, Markus
d5b0b2dd-4018-4fc2-8b31-dbbdefb67ca1
Zhang, Xiaobin
250668b7-bb5d-41a8-8f04-414d4d575a06
Pidchenko, Ivan
948b815c-a3cf-4fae-9d9e-3580f6b60e3c
Hlina, Johann A.
00eb0494-2f0a-4ddb-9724-6ac27954ebcf
Lord, Rianne M.
0aeaa411-8ad5-43f5-a73f-3b42cefd864b
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Nichol, Gary S.
016249ad-f036-477d-9f6e-dd1bc619e372
Magnani, Nicola
39ba7df4-715a-4992-a1f2-052df5bac72e
Schreckenbach, Georg
c7d93e35-34e0-4c57-870d-9a051a85271d
Vitova, Tonya
06bcae55-d7b4-45be-9ea8-7e3f4368309f
Love, Jason B.
86349ecb-c5c7-4151-bd43-d79ddd214b27
Arnold, Polly L.
431d494e-712d-4677-9ee2-0bcefe8a5ca0

Zegke, Markus, Zhang, Xiaobin, Pidchenko, Ivan, Hlina, Johann A., Lord, Rianne M., Purkis, Jamie M., Nichol, Gary S., Magnani, Nicola, Schreckenbach, Georg, Vitova, Tonya, Love, Jason B. and Arnold, Polly L. (2019) Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study. Chemical Science, 10 (42), 9740-9751. (doi:10.1039/C8SC05717F).

Record type: Article

Abstract

The uranyl(VI) ‘Pacman’ complex [(UO2)(py)(H2L)] A (L = polypyrrolic Schiff-base macrocycle) is reduced by Cp2Ti(η2-Me3SiC[triple bond, length as m-dash]CSiMe3) and [Cp2TiCl]2 to oxo-titanated uranyl(V) complexes [(py)(Cp2TiIIIOUO)(py)(H2L)] 1 and [(ClCp2TiIVOUO)(py)(H2L)] 2. Combination of ZrII and ZrIV synthons with A yields the first ZrIV–uranyl(V) complex, [(ClCp2ZrOUO)(py)(H2L)] 3. Similarly, combinations of Ae0 and AeII synthons (Ae = alkaline earth) afford the mono-oxo metalated uranyl(V) complexes [(py)2(ClMgOUO)(py)(H2L)] 4, [(py)2(thf)2(ICaOUO)(py) (H2L)] 5; the zinc complexes [(py)2(XZnOUO)(py)(H2L)] (X = Cl 6, I 7) are formed in a similar manner. In contrast, the direct reactions of Rb or Cs metal with A generate the first mono-rubidiated and mono-caesiated uranyl(V) complexes; monomeric [(py)3(RbOUO)(py)(H2L)] 8 and hexameric [(MOUO)(py)(H2L)]6 (M = Rb 8b or Cs 9). In these uranyl(V) complexes, the pyrrole N–H atoms show strengthened hydrogen-bonding interactions with the endo-oxos, classified computationally as moderate-strength hydrogen bonds. Computational DFT MO (density functional theory molecular orbital) and EDA (energy decomposition analysis), uranium M4 edge HR-XANES (High Energy Resolution X-ray Absorption Near Edge Structure) and 3d4f RIXS (Resonant Inelastic X-ray Scattering) have been used (the latter two for the first time for uranyl(V) in 7 (ZnI)) to compare the covalent character in the UV–O and O–M bonds and show the 5f orbitals in uranyl(VI) complex A are unexpectedly more delocalised than in the uranyl(V) 7 (ZnI) complex. The Oexo–Zn bonds have a larger covalent contribution compared to the Mg–Oexo/Ca–Oexo bonds, and more covalency is found in the U–Oexo bond in 7 (ZnI), in agreement with the calculations.

Text
c8sc05717f - Version of Record
Download (2MB)

More information

Accepted/In Press date: 26 August 2019
e-pub ahead of print date: 6 September 2019
Published date: 14 November 2019

Identifiers

Local EPrints ID: 435932
URI: http://eprints.soton.ac.uk/id/eprint/435932
ISSN: 2041-6520
PURE UUID: 5712ef4f-3712-49ab-9c83-081e395f4019
ORCID for Jamie M. Purkis: ORCID iD orcid.org/0000-0002-6387-1220

Catalogue record

Date deposited: 25 Nov 2019 17:30
Last modified: 26 Nov 2021 03:20

Export record

Altmetrics

Contributors

Author: Markus Zegke
Author: Xiaobin Zhang
Author: Ivan Pidchenko
Author: Johann A. Hlina
Author: Rianne M. Lord
Author: Jamie M. Purkis ORCID iD
Author: Gary S. Nichol
Author: Nicola Magnani
Author: Georg Schreckenbach
Author: Tonya Vitova
Author: Jason B. Love
Author: Polly L. Arnold

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×