Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)]−(An = U, Th; R = SiMe3)

Greggory T. Kent; Xiaojuan Yu; Guang Wu; Jochen Autschbach; Trevor W. Hayton

doi:10.1039/d1sc04666g

Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR₂)₃}An(CCCPh₂)]⁻(An = U, Th; R = SiMe₃)

Greggory T. Kent
, Xiaojuan Yu
, Guang Wu
, Jochen Autschbach
, Trevor W. Hayton

Chemistry

University of California at Santa Barbara
SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

Abstract

The reaction of AnCl(NR₂)₃ (An = U, Th, R = SiMe₃) within situgenerated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR₂)₃}An(CH-C-CPh₂)] (An = U,1; Th,2) in good yields after work-up. Deprotonation of1or2with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR₂)₃}An(CCCPh₂)] (An = U,3; Th,4). The calculated¹³C NMR chemical shifts of the C_α, C_β, and C_γnuclei in2and4nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C_αdue to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for3and4show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C-C-CPh₂) predominates, the An-C-C-CPh₂resonance form contributes, as well, more so for3than for4.

Original language	English
Pages (from-to)	14383-14388
Number of pages	6
Journal	Chemical Science
Volume	12
Issue number	43
DOIs	https://doi.org/10.1039/d1sc04666g
State	Published - Nov 21 2021

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title = "Synthesis and electronic structure analysis of the actinide allenylidenes, [\{(NR2)3\}An(CCCPh2)]−(An = U, Th; R = SiMe3)",

abstract = "The reaction of AnCl(NR2)3 (An = U, Th, R = SiMe3) within situgenerated lithium-3,3-diphenylcyclopropene results in the formation of [\{(NR2)3\}An(CH-C-CPh2)] (An = U,1; Th,2) in good yields after work-up. Deprotonation of1or2with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][\{(NR2)3\}An(CCCPh2)] (An = U,3; Th,4). The calculated13C NMR chemical shifts of the Cα, Cβ, and Cγnuclei in2and4nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at Cαdue to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for3and4show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C-C-CPh2) predominates, the An-C-C-CPh2resonance form contributes, as well, more so for3than for4.",

author = "Kent, \{Greggory T.\} and Xiaojuan Yu and Guang Wu and Jochen Autschbach and Hayton, \{Trevor W.\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021.",

year = "2021",

month = nov,

day = "21",

doi = "10.1039/d1sc04666g",

language = "English",

volume = "12",

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journal = "Chemical Science",

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TY - JOUR

T1 - Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)]−(An = U, Th; R = SiMe3)

AU - Kent, Greggory T.

AU - Yu, Xiaojuan

AU - Wu, Guang

AU - Autschbach, Jochen

AU - Hayton, Trevor W.

PY - 2021/11/21

Y1 - 2021/11/21

N2 - The reaction of AnCl(NR2)3 (An = U, Th, R = SiMe3) within situgenerated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR2)3}An(CH-C-CPh2)] (An = U,1; Th,2) in good yields after work-up. Deprotonation of1or2with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR2)3}An(CCCPh2)] (An = U,3; Th,4). The calculated13C NMR chemical shifts of the Cα, Cβ, and Cγnuclei in2and4nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at Cαdue to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for3and4show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C-C-CPh2) predominates, the An-C-C-CPh2resonance form contributes, as well, more so for3than for4.

AB - The reaction of AnCl(NR2)3 (An = U, Th, R = SiMe3) within situgenerated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR2)3}An(CH-C-CPh2)] (An = U,1; Th,2) in good yields after work-up. Deprotonation of1or2with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR2)3}An(CCCPh2)] (An = U,3; Th,4). The calculated13C NMR chemical shifts of the Cα, Cβ, and Cγnuclei in2and4nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at Cαdue to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for3and4show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C-C-CPh2) predominates, the An-C-C-CPh2resonance form contributes, as well, more so for3than for4.

UR - https://www.scopus.com/pages/publications/85119016928

U2 - 10.1039/d1sc04666g

DO - 10.1039/d1sc04666g

M3 - Article

AN - SCOPUS:85119016928

SN - 2041-6520

VL - 12

SP - 14383

EP - 14388

JO - Chemical Science

JF - Chemical Science

IS - 43

ER -

Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR₂)₃}An(CCCPh₂)]⁻(An = U, Th; R = SiMe₃)

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