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The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

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The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. / Gregson, Matthew; Lu, Erli; Mills, David et al.
In: Nature Communications, Vol. 8, 14137, 03.02.2017.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Gregson, M, Lu, E, Mills, D, Tuna, F, McInnes, E, Hennig, C, Scheinost, A, McMaster, J, Lewis, W, Blake, A, Kerridge, A & Liddle, S 2017, 'The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes', Nature Communications, vol. 8, 14137. https://doi.org/10.1038/ncomms14137

APA

Gregson, M., Lu, E., Mills, D., Tuna, F., McInnes, E., Hennig, C., Scheinost, A., McMaster, J., Lewis, W., Blake, A., Kerridge, A., & Liddle, S. (2017). The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications, 8, Article 14137. https://doi.org/10.1038/ncomms14137

Vancouver

Gregson M, Lu E, Mills D, Tuna F, McInnes E, Hennig C et al. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications. 2017 Feb 3;8:14137. doi: 10.1038/ncomms14137

Author

Gregson, Matthew ; Lu, Erli ; Mills, David et al. / The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. In: Nature Communications. 2017 ; Vol. 8.

Bibtex

@article{c79799c5a72545b48db8b3a3e3290706,
title = "The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes",
abstract = "Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.",
author = "Matthew Gregson and Erli Lu and David Mills and Floriana Tuna and Eric McInnes and Cristoph Hennig and Andreas Scheinost and Jonathan McMaster and William Lewis and Alexander Blake and Andrew Kerridge and Stephen Liddle",
year = "2017",
month = feb,
day = "3",
doi = "10.1038/ncomms14137",
language = "English",
volume = "8",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Nature Publishing Group",

}

RIS

TY - JOUR

T1 - The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

AU - Gregson, Matthew

AU - Lu, Erli

AU - Mills, David

AU - Tuna, Floriana

AU - McInnes, Eric

AU - Hennig, Cristoph

AU - Scheinost, Andreas

AU - McMaster, Jonathan

AU - Lewis, William

AU - Blake, Alexander

AU - Kerridge, Andrew

AU - Liddle, Stephen

PY - 2017/2/3

Y1 - 2017/2/3

N2 - Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

AB - Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

U2 - 10.1038/ncomms14137

DO - 10.1038/ncomms14137

M3 - Journal article

VL - 8

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

M1 - 14137

ER -