Perutz, Robin Noel orcid.org/0000-0001-6286-0282, Pike, Sarah Jane, Brammer, Lee et al. (1 more author) (2019) Benchmarking of Halogen Bond Strength in Solution with Nickel Fluorides:Bromine versus Iodine and Perfluoroaryl versus Perfluoroalkyl Donors. Chemistry : A European Journal. chem.201900924R1. pp. 9237-9241. ISSN 1521-3765
Abstract
The energetics of halogen bond formation in solution have been investigated for a series of nickel fluoride halogen bond acceptors; trans-[NiF(2-C 5NF 4)(PEt 3) 2] (A1), trans-[NiF{2-C 5NF 3(4-H)}(PEt 3) 2] (A2), trans-[NiF{2-C 5NF 3(4-NMe 2)}(PEt 3) 2] (A3) and trans-[NiF{2-C 5NF 2H(4-CF 3)}(PCy 3) 2] (A4) with neutral organic halogen bond donors, iodopentafluorobenzene (D1), 1-iodononafluorobutane (D2) and bromopentafluorobenzene (D3), in order to establish the significance of changes from perfluoroaryl to perfluoroalkyl donors and from iodine to bromine donors. 19F NMR titration experiments have been employed to obtain the association constants, enthalpy, and entropy for the halogen bond formed between these donor-acceptor partners in protiotoluene. For A2–A4, association constants of the halogen bonds formed with iodoperfluoroalkane (D2) are consistently larger than those obtained for analogous complexes with the iodoperfluoroarene (D1). For complexes formed with A2–A4, the strength of the halogen bond is significantly lowered upon modification of the halogen donor atom from I (in D1) to Br (in D3) (for D1: 5≤K 285≤12 m −1, for D3: 1.0≤K 193≤1.6 m −1). The presence of the electron donating NMe 2 substituent on the pyridyl ring of acceptor A3 led to an increase in −ΔH, and the association constants of the halogen bond complexes formed with D1–D3, compared to those formed by A1, A2 and A4 with the same donors.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2019 WILEY‐VCH Verlag GmbH & Co. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Keywords: | NMR spectroscopy,halogen bonds,nickel fluorides,perfluoroaryl and perfluoroalkyl donors,solution |
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 15 Apr 2019 15:50 |
Last Modified: | 07 Feb 2025 00:24 |
Published Version: | https://doi.org/10.1002/chem.201900924 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1002/chem.201900924 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:145012 |
Download
Filename: Manuscript_Benchmarking_halogen_bonds.pdf
Description: Manuscript Benchmarking halogen bonds