Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Ordoñez, Osvaldo; Yu, Xiaojuan; Wu, Guang; Autschbach, Jochen; Hayton, Trevor W.

doi:10.1021/acs.inorgchem.1c01686

Title: Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Journal Article · Fri Jul 30 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c01686· OSTI ID:1864779

Ordoñez, Osvaldo ^[1];

^[2]; Wu, Guang ^[1];

^[2];

^[1]

Univ. of California, Santa Barbara, CA (United States)
Univ. at Buffalo, State Univ. of New York, NY (United States)

The reaction of AnCl₄(DME)_n (An = Th, n = 2; U, n = 0) with 5 equiv of LiC₆Cl₅ in Et₂O resulted in the formation of homoleptic actinide-aryl “ate” complexes [Li(DME)₂(Et₂O)]₂[Li(DME)₂][Th(C₆Cl₅)₅]₃ ([Li][1]) and [Li(Et₂O)₄][U(C₆Cl₅)₅] ([Li][2]). Similarly, the reaction of AnCl₄(DME)n (An = Th, n = 2; U, n = 0) with 3 equiv of LiC₆Cl₅ in Et₂O resulted in the formation of heteroleptic actinide-aryl “ate” complexes [Li(DME)₂(Et₂O)][Li(Et₂O)₂][ThCl₃(C₆Cl₅)₃] ([Li][3]) and [Li(Et₂O)₃][UCl₂(C₆Cl₅)₃] ([Li][4]). Density functional calculations show that the An–C_ipso σ-bonds are considerably more covalent for the uranium complexes vs the thorium analogues, in line with past results. Additionally, good agreement between experiment and calculations is obtained for the ¹³C_ipso NMR chemical shifts in [Li][1] and [Li][3]. Here, the calculations demonstrate a deshielding by ca. 29 ppm from spin–orbit coupling effects originating at Th, which is a direct consequence of 5f orbital participation in the Th–C bonds.

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Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001861

OSTI ID:: 1864779

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 16; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

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