Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural MotifsCitation formats

  • Authors:
  • Elizabeth Wildman
  • Gabor Balazs
  • Ashley Wooles
  • Manfred Scheer
  • Stephen Liddle

Standard

Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural Motifs. / Wildman, Elizabeth; Balazs, Gabor; Wooles, Ashley; Scheer, Manfred; Liddle, Stephen.

In: Nature Communications, Vol. 8, 14769, 2017.

Research output: Contribution to journalArticle

Harvard

APA

Vancouver

Author

Wildman, Elizabeth ; Balazs, Gabor ; Wooles, Ashley ; Scheer, Manfred ; Liddle, Stephen. / Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural Motifs. In: Nature Communications. 2017 ; Vol. 8.

Bibtex

@article{2956aaad2d7248c4b1715061044cb4ab,
title = "Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural Motifs",
abstract = "Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.",
author = "Elizabeth Wildman and Gabor Balazs and Ashley Wooles and Manfred Scheer and Stephen Liddle",
year = "2017",
doi = "10.1038/ncomms14769",
language = "English",
volume = "8",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Springer Nature",

}

RIS

TY - JOUR

T1 - Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural Motifs

AU - Wildman, Elizabeth

AU - Balazs, Gabor

AU - Wooles, Ashley

AU - Scheer, Manfred

AU - Liddle, Stephen

PY - 2017

Y1 - 2017

N2 - Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

AB - Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

U2 - 10.1038/ncomms14769

DO - 10.1038/ncomms14769

M3 - Article

VL - 8

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

M1 - 14769

ER -