White phosphorus activation by a Th(iii) complex

Abstract

[Th(Cp'')3] (Cp'' = {C5H3(SiMe3)2-1,3}) activates P4 to give [{Th(Cp'')3}2(μ-η(1):η(1)-P4)] (1), which has an unprecedented cyclo-P4 binding mode. DFT studies were performed on a model of 1 to probe the bonding in this system.

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

“…For example, under ambient conditions there are only a handful of each class of structurally authenticated formal Th=C carbene134445, Th=N imido464748 and terminal Th=O oxo or Th=E···K (E=O, S, Se, Te) complexes495051 known; where thorium–phosphorus multiple bonds are concerned, they are conspicuous by their absence outside of cryogenic matrix isolation experiments52. Indeed, of fewer than thirty crystallographically authenticated thorium–phosphorus complexes in the Cambridge Structural Database53 seven are phosphanides54555657585960, three are polyphosphides6162, one is a phosphinidiide54, a term we use to indicate its bridging nature, and the remainder are phosphine derivatives; a dithorium-phosphinidiide complex [{Th(η 5 -C 5 Me 5 ) 2 (OMe)} 2 (μ-PH)] (ref. 36) has been described though not structurally confirmed.…”

Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex

“…The mapping of U III ‐mediated CO 2 activation by DFT calculations has provided key insights into possible mechanistic pathways . In contrast, Cloke reported the only example of CO 2 activation by a putative Th III intermediate as Th III small molecule activation is in its infancy . Herein we report the first reaction of an isolated Th III complex with CO 2 , and CS 2 for comparative studies.…”

Quantification of f-element covalency through analysis of the electron density: insights from simulation

“…Already-realised applications of QTAIM in f-element chemistry include the quantification and nature of bond-covalency and stability, oxidation state identification, and similarities/differences in lanthanide and actinide bonding. Potential future developments might include the ability to analyse spin-orbit 6 ] nÀ (n = 0-3) 65 +6, +5, +4, +3 +5.75, +5.12, +4.25, +3.38 An(E 2 PL 2 ) 4 (An = Th; U, E = S, Se; L= t Bu, i Pr) 83 +4 +4.15-+4.29 M(BIPM TMS )(ODipp) 2 (M = Ce, Th, U) 11 +4 +4.26-+4.39 M(BIPM TMS ) 2 (M = Ce, Th, U) 12 +4 +4.17-+4.34 {Th-(Cp 00 ) 3 } 2 (m-Z 1 :Z 1 -P 4 ), 84 {Th(Cp 000 ) 2 [k 2 -O 2 C{C 5 H 3 -3,3 0 -(SiMe 3 ) 2 }]} 2 (m-k 2 :k 2 -C 2 O 4 ), 85 [{Th(Cp 00 ) 3 coupled densities and more importantly, a rigorous approach to energy decomposition. While a framework for such energy decomposition exists, the Interacting Quantum Atom (IQA) approach of Blanco et al, 98 current implementations are not generally applicable to all exchange-correlation functionals, or to relativistic Hamiltonians.…”