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Title: Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Abstract

Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene—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 Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead. 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. Finally, 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.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [4];  [3];  [3];  [5];  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States); Beijing Inst. of Technology (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Vermont, Burlington, VT (United States)
  5. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1605163
Grant/Contract Number:  
SC0002183; CHE-1265608; CHE-1565658; AC06-05OR231100; AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 578; Journal Issue: 7796; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; organometallic chemistry

Citation Formats

Pagano, Justin K., Xie, Jing, Erickson, Karla A., Cope, Stephen K., Scott, Brian L., Wu, Ruilian, Waterman, Rory, Morris, David E., Yang, Ping, Gagliardi, Laura, and Kiplinger, Jaqueline L. Actinide 2-metallabiphenylenes that satisfy Hückel’s rule. United States: N. p., 2020. Web. doi:10.1038/s41586-020-2004-7.
Pagano, Justin K., Xie, Jing, Erickson, Karla A., Cope, Stephen K., Scott, Brian L., Wu, Ruilian, Waterman, Rory, Morris, David E., Yang, Ping, Gagliardi, Laura, & Kiplinger, Jaqueline L. Actinide 2-metallabiphenylenes that satisfy Hückel’s rule. United States. doi:https://doi.org/10.1038/s41586-020-2004-7
Pagano, Justin K., Xie, Jing, Erickson, Karla A., Cope, Stephen K., Scott, Brian L., Wu, Ruilian, Waterman, Rory, Morris, David E., Yang, Ping, Gagliardi, Laura, and Kiplinger, Jaqueline L. Wed . "Actinide 2-metallabiphenylenes that satisfy Hückel’s rule". United States. doi:https://doi.org/10.1038/s41586-020-2004-7. https://www.osti.gov/servlets/purl/1605163.
@article{osti_1605163,
title = {Actinide 2-metallabiphenylenes that satisfy Hückel’s rule},
author = {Pagano, Justin K. and Xie, Jing and Erickson, Karla A. and Cope, Stephen K. and Scott, Brian L. and Wu, Ruilian and Waterman, Rory and Morris, David E. and Yang, Ping and Gagliardi, Laura and Kiplinger, Jaqueline L.},
abstractNote = {Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene—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. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead. 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. Finally, 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.},
doi = {10.1038/s41586-020-2004-7},
journal = {Nature (London)},
number = 7796,
volume = 578,
place = {United States},
year = {2020},
month = {2}
}

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