Portal de Periódicos da CAPES

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

2017; Nature Portfolio; Volume: 8; Issue: 1 Linguagem: Inglês

10.1038/ncomms14137

2041-1723

Matthew Gregson, Erli Lu, David P. Mills, Floriana Tuna, Eric J. L. McInnes, Christoph Hennig, Andreas C. Scheinost, Jonathan McMaster, William Lewis, Alexander J. Blake, Andrew Kerridge, Stephen T. Liddle,

Organometallic Complex Synthesis and Catalysis

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.