ChemInform Abstract: AN ORGANOTHORIUM‐NICKEL PHOSPHIDO COMPLEX WITH A SHORT THORIUM‐NICKEL DISTANCE. THE STRUCTURE OF TH(η5‐C5ME5)2(μ‐PPH2)2NI(CO)2

Abstract

Der Titelkomplex (III) ent‐′ steht durch die angegebene 1:1‐molare Reaktion und wird IR‐, UV/VIS‐ und 1H‐ sowie 31P‐NMR‐spektroskopisch charakterisiert.

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

“…The Th–P bond distance in 2 is in good agreement with the sum of the single-bond covalent radii for thorium and phosphorus67, but is relatively long for a thorium(IV)–phosphanide bond545556575859. However, this can be rationalized on the sterically demanding Tren TIPS ligand whereas all other thorium(IV)–phosphanide complexes involve a bis (pentamethylcyclopentadienyl) ligand combination that presents a sterically more accessible wedge for phosphanide ligation545556575859. Interestingly, the Th–P bond is ∼0.05 Å longer than might be expected from the difference in covalent radii of thorium and uranium67 when compared with the parent uranium(IV)–phosphanide congener34, which may reflect a more ionic Th–P interaction compared with the U–P interaction as suggested by calculations (see below).…”

“…2.866 Å), [Th(η 5 -C 5 Me 5 ) 2 {P(SiMe 3 ) 2 }(Me)] (2.888(4) Å) and [Th(η 5 -C 5 Me 5 ) 2 (HP-2,4,6-Pr i 3 C 6 H 2 ) 2 ] (av. 2.879 Å) (refs 54, 55, 56, 57, 58, 59). The Th–P distance in 2 can also be compared with the U-P distance in the uranium analogue (2.883(2) Å) (ref.…”

“…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.…”

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

“…In order to ascertain whether this is a unique or more broadly applicable phenomenon would require comparison to closely related compounds and in that regard arsenic congeners are the logical next step. However, reflecting the cumulative instability of pairing a large, polar metal like thorium with increasingly large, soft p-block elements394041424344454647 presents an increasing synthetic challenge regarding their preparation and isolation. Indeed, examples of thorium complexes with bonds to pnictide (Pn) elements heavier than phosphorus are exceedingly rare, and under ambient conditions the only two structurally characterized thorium–arsenic complexes are the Zintl-polyarsenide [{Th(η 5 -1,3-Bu t 2 C 5 H 3 ) 2 } 2 (μ-η 3 :η 3 -As 6 )] (ref.…”