Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

Abstract

Structural, spectroscopic and theoretical analyses of mer-MBr3(OPcy3)3 (M = Am, Nd, Pr, Ce, La) reveal significant amounts of metal based p-orbital contribution.

Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules

“…Splitting of the higher energy peak is not always observed, but was reported for [Am(Cp tet ) 3 ], and was reproduced by SO‐CASSCF/NEVPT2 calculations; the splitting was rationalized by increased splitting of excited crystal field states [12d] . Other Am 3+ complexes that show comparable peak splitting have O‐donor ligands such as: poly‐borate anions for example, {B 9 O 13 (OH) 4 }, [30] or neutral O‐donor ligands for example, O=PCy 3 [25b, 31] . It is likely that this splitting derives not just from ligand field effects, but also solution/solid phase symmetry differences and vibronic coupling [29, 32] .…”

[AnI3(THF)4] (An = Np, Pu) Preparation Bypassing An0 Metal Precursors: Access to Np3+/Pu3+ Nonaqueous and Organometallic Complexes

“…Note that, in principle, AnO 2 (An = Np, Pu) could be dissolved in HI (aq) to directly produce An 3+ (aq) , similar to the previously mentioned synthesis of [PuBr 3 (DME) 2 ]. 55 Such a route is likely a viable approach for the transplutonium elements Cm−Cf due to the stability of their trivalent oxidation state, 7,8,107,108 and it has been demonstrated with the synthesis of [AmBr 3 (THF) 4 ] by the dissolution of AmO 2 . 107 However, the relative redox instability of Np 3+ , coupled with the desire to develop homologous routes to both Np 3+ and Pu 3+ starting materials, led us to the methods herein.…”

“…The scientific understanding of the role that f-electrons play in the bonding, electronic structure, − redox chemistry, − and physics of the actinides (An) is continually evolving. ,, Widespread advances over the last 30 years have remapped the known boundaries of molecular Th and, in particular, U molecular chemistry. Progress has ranged from the discovery of new oxidation states (An 2+ ; An = Th, U, Np, Pu) ,− ,, to an array of non-actinyl multiple-bond chemistry, − ,− to covalency studies ,,,− and small molecule reactivity. ,, An expanding and diverse synthetic “toolbox” of nonaqueous, organic solvent soluble Th/U starting materials has been key in facilitating the explosion of molecular chemistry studies for these early actinide elements.…”

A Trivalent Americium Organic Framework with Decent Structural Stability against Self‐Irradiation

“…Phosphine oxides are highly stable ligands which have strong extraction ability but a moderate selectivity toward the trivalent actinides over lanthanides in the highly acidic nitrate solution. [ 11 ] Therefore, utilizing the organic ligand with phosphonyl group as linker to explore the difference between Am 3+ and lanthanide in MOFs system may be a feasible way. Herein, we report the synthesis methods, structural elucidation and UV–vis–NIR spectrum of a new Am 3+ ‐based MOF, AmTPO (TPO = tris(4‐carboxylphenyl)‐ phosphineoxide), under mild solvothermal condition via using H 3 TPO, which has both of carboxyl and phosphonyl groups as organic linker.…”