ORCID Profile
0000-0002-0619-5967
Current Organisation
Newcastle University
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Publisher: Wiley
Date: 15-10-2013
Abstract: Straightforward access to a cerium(IV)-carbene complex was provided by one-electron oxidation of an anionic "ate" cerium(III)-carbene precursor, thereby avoiding decomposition reactions that plague oxidations of neutral cerium(III) compounds. The cerium(IV)-carbene complex is the first lanthanide(IV)-element multiple bond and involves a twofold bonding interaction of two electron pairs between cerium and carbon.
Publisher: Wiley
Date: 07-07-2014
Publisher: Springer Science and Business Media LLC
Date: 03-02-2017
DOI: 10.1038/NCOMMS14137
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 4 f orbitals are populated. This work suggests that the inverse- trans -influence may occur beyond high oxidation state 5 f 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.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6SC00278A
Abstract: Against expectations the covalency in a cerium( iv )–carbon multiple bond interaction is essentially as covalent as the uranium( iv ) analogue.
Publisher: Wiley
Date: 19-05-2014
Publisher: Wiley
Date: 12-07-2016
Abstract: We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM(TMS) )(NCPh3 )(NHCPh3 )(M)] (BIPM(TMS) =C(PPh2 NSiMe3 )2 M=Li or K) that can be described as R2 C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R2 C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U(IV) =N units.
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
No related grants have been discovered for Erli Lu.