Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives

Literature Information

Publication Date 2020-05-05
DOI 10.1039/D0CP01481H
Impact Factor 3.676
Authors

Jan Vícha, Abhik Ghosh


View Original

Abstract

We have studied the magnetic response properties and aromaticity of osmium metallacycles by means of scalar-relativistic (1c) and fully relativistic (4c) density functional theory computations. For osmabenzene, whose aromatic character is controversial, a topological analysis of the current density has revealed the presence of a unique σ-type Craig–Möbius magnetic aromaticity. We show that the partially filled osmium valence shell induces a large paratropic current, which may interfere with certain methods commonly used to analyze aromaticity, in particular NICS. Further, we show that the extreme deshielding of the light atoms in the vicinity of the osmium atoms in osmapentalene derivatives is not a consequence of aromaticity but can be explained by paramagnetic couplings between σOs—C bonding orbitals and the π*Os orbitals. We demonstrate that variations in the orientation of the induced magnetic currents through the molecule dictates the alternating signs of the spin–orbit contribution to the NMR chemical shift.

Related Literature

Polymerization-induced self-assembly of PVAc-b-PVDF block copolymers via RAFT dispersion polymerization of vinylidene fluoride in dimethyl carbonate

Marc Guerre, Mona Semsarilar, Franck Godiard, Bruno Améduri, Vincent Ladmiral

2017-01-20 Paper

DOI: 10.1039/C6PY02203K

Heterogeneous organocatalysts composed of microporous polymer networks assembled by Tröger's base formation

Mariolino Carta, Matthew Croad, Keith Bugler, Kadhum J. Msayib, Neil B. McKeown

2014-06-20 Paper

DOI: 10.1039/C4PY00608A

The para-fluoro-thiol ligation in water

Parvesh Wadhwani, Rouven Müller

2017-01-16 Communication

DOI: 10.1039/C6PY02108E

Free-standing thermo-responsive nanoporous membranes from high molecular weight PS-PNIPAM block copolymers synthesized via RAFT polymerization

Merve Mocan, Joris de Grooth, Anton H. Hofman, Hanne M. van der Kooij, Katja Loos, Wiebe M. de Vos, Marleen Kamperman

2017-03-17 Paper

DOI: 10.1039/C7PY00023E

Vesicles of double hydrophilic pullulan and poly(acrylamide) block copolymers: a combination of synthetic- and bio-derived blocks

Jochen Willersinn, Anna Bogomolova, Marc Brunet Cabré, Bernhard V. K. J. Schmidt

2017-01-09 Paper

DOI: 10.1039/C6PY02212J

Synthesis of highly branched polymers by reversible complexation-mediated copolymerization of vinyl and divinyl monomers

Hongjun Yang, Zhongrui Wang, Yulei Zheng, Wenyan Huang, Xiaoqiang Xue, Bibiao Jiang

2017-02-21 Paper

DOI: 10.1039/C7PY00174F

tBCPMA: a new trifunctional acrylic monomer for convenient synthesis of a well-defined amphiphilic graft copolymer by successive RDRP

Chun Feng, Guolin Lu, Gang Sun, Xunwei Liu, Xiaoyu Huang

2014-06-30 Paper

DOI: 10.1039/C4PY00772G

You might also like

Compound Q&A

What are the main uses of 4-Nitrophenyl phosphate disodium salt hexahydrate (CAS: 333338-18-4)?

4-Nitrophenyl phosphate disodium salt hexahydrate is primarily used as a substra...

333338-18-44-Nitrophenyl phosph...
Compound Q&A

What are the main uses of 2-(Trifluoromethyl)-1,3-oxazole-4-carboxylic Acid (CAS: 1060816-01-4)?

2-(Trifluoromethyl)-1,3-oxazole-4-carboxylic Acid (CAS: 1060816-01-4) is widely ...

1060816-01-42-(Trifluoromethyl)-...
Compound Q&A

How should 2-Fluoro-4-biphenylcarboxylic acid (CAS: 137045-30-8) be stored?

2-Fluoro-4-biphenylcarboxylic acid should be stored in a cool, dry place at room...

137045-30-82-Fluoro-4-biphenylc...
Compound Q&A

What industries use Prednisolone-21-Carboxylic Acid (CAS: 61549-70-0)?

Prednisolone-21-Carboxylic Acid is primarily used in the pharmaceutical industry...

61549-70-0Prednisolone-21-Carb...
Compound Q&A

How should 4-(Hydrazinomethyl)-1,2,3-benzenetriol (CAS: 3614-72-0) be stored?

4-(Hydrazinomethyl)-1,2,3-benzenetriol (CAS: 3614-72-0) should be stored in a co...

3614-72-04-(Hydrazinomethyl)-...
Compound Q&A

What industries use 4-Amino-1-methyl-1H-pyrazole-5-carboxylic acid hydrochloride (CAS: 92534-70-8)?

4-Amino-1-methyl-1H-pyrazole-5-carboxylic acid hydrochloride (CAS: 92534-70-8) i...

92534-70-84-Amino-1-methyl-1H-...
Compound Q&A

What regulatory guidelines apply to dehydropachymic acid (CAS: 77012-31-8)?

Dehydropachymic acid (CAS: 77012-31-8) is regulated by various agencies. It fall...

77012-31-8Dehydropachymic acid
Compound Q&A

What is the market or research trend for 6-[(2,2-Dimethylpropanoyl)amino]nicotinic acid (CAS: 898561-66-5)?

The market and research trends for 6-[(2,2-Dimethylpropanoyl)amino]nicotinic aci...

898561-66-56-[(2,2-Dimethylprop...
Compound Q&A

How should 1,10-Phenanthroline-2,9-dicarbaldehyde (CAS: 57709-62-3) be stored?

1,10-Phenanthroline-2,9-dicarbaldehyde should be stored in a cool, dry place awa...

57709-62-31,10-Phenanthroline-...
Compound Q&A

How is 5-Carbamoyl-11-oxo-10,11-dihydro-5H-dibenzo[b,f]azepin-10-yl acetate (CAS: 113952-21-9) typically synthesized?

5-Carbamoyl-11-oxo-10,11-dihydro-5H-dibenzo[b,f]azepin-10-yl acetate can be synt...

113952-21-95-Carbamoyl-11-oxo-1...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.