Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Justin K. Pagano; Jing Xie; Karla A. Erickson; Stephen K. Cope; Brian L. Scott; Ruilian Wu; Rory Waterman; David E. Morris; Ping Yang; Laura Gagliardi; Jaqueline L. Kiplinger

doi:10.1038/s41586-020-2004-7

Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Justin K. Pagano, Jing Xie, Karla A. Erickson, Stephen K. Cope, Brian L. Scott, Ruilian Wu, Rory Waterman, David E. Morris, Ping Yang, Laura Gagliardi, Jaqueline L. Kiplinger

Chemistry (Twin Cities)

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

50 Scopus citations

Abstract

Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene^1–3—a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds^4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead⁶. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn–Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f² electrons with the carbon-containing ligand.

Original language	English (US)
Pages (from-to)	563-567
Number of pages	5
Journal	Nature
Volume	578
Issue number	7796
DOIs	https://doi.org/10.1038/s41586-020-2004-7
State	Published - Feb 27 2020

Bibliographical note

Funding Information:
Acknowledgements For financial support of this work, we acknowledge the US Department of Energy (DOE) through the Los Alamos National Laboratory (LANL) Laboratory Directed Research and Development Program; the LANL G. T. Seaborg Institute for Transactinium Science (Postdoctoral Fellowships to J.K.P., K.A.E. and S.K.C.); the Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program (GRA Fellowship to J.K.P.); and the Office of Basic Energy Sciences, Heavy Element Chemistry program (to J.L.K., P.Y. and B.L.S., for materials and supplies). We thank R. Michalczyk and L. A. Silks (LANL) for assistance with two-dimensional NMR experiments, and J. Thompson and P. Rosa (LANL) for assistance in collecting magnetometry data. This work was in part funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US DOE through grant USDOE/ DESC002183 (to J.X. and L.G.). We also acknowledge the US National Science Foundation (grants CHE-1265608 and CHE-1565658 to R. Waterman). The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE (contract DE-AC05-06OR23100). LANL is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the US DOE (contract DE-AC52-06NA25396).

Publisher Copyright:
© 2020, The Author(s), under exclusive licence to Springer Nature Limited.

Publisher link

10.1038/s41586-020-2004-7

Find It

Find It at U of M Libraries

Cite this

@article{0867dff15c8b463eb1b8edfd9d62be59,

title = "Actinide 2-metallabiphenylenes that satisfy H{\"u}ckel{\textquoteright}s rule",

abstract = "Aromaticity and antiaromaticity, as defined by H{\"u}ckel{\textquoteright}s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene1–3—a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead6. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn–Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f2 electrons with the carbon-containing ligand.",

author = "Pagano, {Justin K.} and Jing Xie and Erickson, {Karla A.} and Cope, {Stephen K.} and Scott, {Brian L.} and Ruilian Wu and Rory Waterman and Morris, {David E.} and Ping Yang and Laura Gagliardi and Kiplinger, {Jaqueline L.}",

note = "Funding Information: Acknowledgements For financial support of this work, we acknowledge the US Department of Energy (DOE) through the Los Alamos National Laboratory (LANL) Laboratory Directed Research and Development Program; the LANL G. T. Seaborg Institute for Transactinium Science (Postdoctoral Fellowships to J.K.P., K.A.E. and S.K.C.); the Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program (GRA Fellowship to J.K.P.); and the Office of Basic Energy Sciences, Heavy Element Chemistry program (to J.L.K., P.Y. and B.L.S., for materials and supplies). We thank R. Michalczyk and L. A. Silks (LANL) for assistance with two-dimensional NMR experiments, and J. Thompson and P. Rosa (LANL) for assistance in collecting magnetometry data. This work was in part funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US DOE through grant USDOE/ DESC002183 (to J.X. and L.G.). We also acknowledge the US National Science Foundation (grants CHE-1265608 and CHE-1565658 to R. Waterman). The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE (contract DE-AC05-06OR23100). LANL is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the US DOE (contract DE-AC52-06NA25396). Publisher Copyright: {\textcopyright} 2020, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2020",

month = feb,

day = "27",

doi = "10.1038/s41586-020-2004-7",

language = "English (US)",

volume = "578",

pages = "563--567",

journal = "Nature",

issn = "0028-0836",

publisher = "Nature Research",

number = "7796",

}

TY - JOUR

T1 - Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

AU - Pagano, Justin K.

AU - Xie, Jing

AU - Erickson, Karla A.

AU - Cope, Stephen K.

AU - Scott, Brian L.

AU - Wu, Ruilian

AU - Waterman, Rory

AU - Morris, David E.

AU - Yang, Ping

AU - Gagliardi, Laura

AU - Kiplinger, Jaqueline L.

N1 - Funding Information: Acknowledgements For financial support of this work, we acknowledge the US Department of Energy (DOE) through the Los Alamos National Laboratory (LANL) Laboratory Directed Research and Development Program; the LANL G. T. Seaborg Institute for Transactinium Science (Postdoctoral Fellowships to J.K.P., K.A.E. and S.K.C.); the Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program (GRA Fellowship to J.K.P.); and the Office of Basic Energy Sciences, Heavy Element Chemistry program (to J.L.K., P.Y. and B.L.S., for materials and supplies). We thank R. Michalczyk and L. A. Silks (LANL) for assistance with two-dimensional NMR experiments, and J. Thompson and P. Rosa (LANL) for assistance in collecting magnetometry data. This work was in part funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US DOE through grant USDOE/ DESC002183 (to J.X. and L.G.). We also acknowledge the US National Science Foundation (grants CHE-1265608 and CHE-1565658 to R. Waterman). The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE (contract DE-AC05-06OR23100). LANL is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the US DOE (contract DE-AC52-06NA25396). Publisher Copyright: © 2020, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2020/2/27

Y1 - 2020/2/27

N2 - Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene1–3—a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead6. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn–Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f2 electrons with the carbon-containing ligand.

AB - Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene1–3—a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead6. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn–Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f2 electrons with the carbon-containing ligand.

UR - http://www.scopus.com/inward/record.url?scp=85080044086&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85080044086&partnerID=8YFLogxK

U2 - 10.1038/s41586-020-2004-7

DO - 10.1038/s41586-020-2004-7

M3 - Article

C2 - 32103196

AN - SCOPUS:85080044086

SN - 0028-0836

VL - 578

SP - 563

EP - 567

JO - Nature

JF - Nature

IS - 7796

ER -

Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Abstract

Bibliographical note

Publisher link

Find It

Other files and links

Fingerprint

Cite this