A Computational Study into the Mechanism of B–B Bond Cleavage in a Magnesium(II) Diboranate Complex

Claire McMullin, Sam Neale, Georgia L. Young

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2 Citations (SciVal)

Abstract

The breaking of the asymmetric B–B bond within a Mg(II) diboranate complex, [Mg](pinBB(nBu)pin) when [(MeBDIDipp)Mg] = [Mg], in the presence of DMAP (4-dimethylaminopyridine), is analyzed with DFT (Density Functional Theory) and NBO (Natural Bond Orbital) methods. The formation of a magnesium-boryl species, [Mg](Bpin)(DMAP)], which exhibits boron “umpolung” nucleophilic behaviour, is explored through “inner” and “outer” sphere mechanisms, alongside a spontaneous base capture pathway. Charges, bond occupancies, Frontier Orbitals and a steric parameter are used to rationalise the mechanistic features of the system, as well as various reactivity observations. Functional testing results and attempts to model unusual 11B NMR data are also reported.
Original languageEnglish
Article numbere202300393
JournalEuropean Journal of Inorganic Chemistry
Volume27
Issue number1
Early online date13 Oct 2023
DOIs
Publication statusPublished - 2 Jan 2024

Bibliographical note

CLM and SEN thank the EPSRC for funding (EP/R020752). CLM also thanks the Royal Society of Chemistry for a Research Enablement Grant (E21-8355738114). GLY was a recipient of the University of Bath Andrey Berzins Gold Scholarship, she also thanks the Department of Chemistry at the University of Bath for project student funding.

Funding Information:
This work would not have been possible if it weren't for Professor Mike Hill and his group busily synthesising all kinds of fun compounds. Thanks to all whose experimental work on magnesium boryls has shaped this project (Anne‐Fred P., Cath W., Annie C., Grace M., Bibian O.‐E., Max D. Louis M. and Henry S.), and of course to Mike for leading us. Thanks also to Dr Mary Mahon for all her crystallography knowledge that has provided structures to compute, and to Dr Nasir Rajabi who significantly contributed to the previous computational mechanistic studies. CLM and SEN thank the EPSRC for funding (EP/R020752). CLM also thanks the Royal Society of Chemistry for a Research Enablement Grant (E21‐8355738114). GLY was a recipient of the University of Bath Andrey Berzins Gold Scholarship, she also thanks the Department of Chemistry at the University of Bath for project student funding. This research made use of the Balena and Anatra High Throughput Computing (HTC) Clusters at the University of Bath. The authors gratefully acknowledge the University of Bath's Research Computing Group (doi.org/10.15125/b6cd‐s854) for their support in this work.

Funding

This work would not have been possible if it weren't for Professor Mike Hill and his group busily synthesising all kinds of fun compounds. Thanks to all whose experimental work on magnesium boryls has shaped this project (Anne‐Fred P., Cath W., Annie C., Grace M., Bibian O.‐E., Max D. Louis M. and Henry S.), and of course to Mike for leading us. Thanks also to Dr Mary Mahon for all her crystallography knowledge that has provided structures to compute, and to Dr Nasir Rajabi who significantly contributed to the previous computational mechanistic studies. CLM and SEN thank the EPSRC for funding (EP/R020752). CLM also thanks the Royal Society of Chemistry for a Research Enablement Grant (E21‐8355738114). GLY was a recipient of the University of Bath Andrey Berzins Gold Scholarship, she also thanks the Department of Chemistry at the University of Bath for project student funding. This research made use of the Balena and Anatra High Throughput Computing (HTC) Clusters at the University of Bath. The authors gratefully acknowledge the University of Bath's Research Computing Group (doi.org/10.15125/b6cd‐s854) for their support in this work. This work would not have been possible if it weren't for Professor Mike Hill and his group busily synthesising all kinds of fun compounds. Thanks to all whose experimental work on magnesium boryls has shaped this project (Anne-Fred P., Cath W., Annie C., Grace M., Bibian O.-E., Max D. Louis M. and Henry S.), and of course to Mike for leading us. Thanks also to Dr Mary Mahon for all her crystallography knowledge that has provided structures to compute, and to Dr Nasir Rajabi who significantly contributed to the previous computational mechanistic studies. CLM and SEN thank the EPSRC for funding (EP/R020752). CLM also thanks the Royal Society of Chemistry for a Research Enablement Grant (E21-8355738114). GLY was a recipient of the University of Bath Andrey Berzins Gold Scholarship, she also thanks the Department of Chemistry at the University of Bath for project student funding. This research made use of the Balena and Anatra High Throughput Computing (HTC) Clusters at the University of Bath. The authors gratefully acknowledge the University of Bath's Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.

FundersFunder number
Engineering and Physical Sciences Research CouncilEP/R020752
Royal Society of ChemistryE21‐8355738114
University of Bath

Keywords

  • Bond cleavage
  • Boron
  • Density functional calculations
  • Magnesium
  • Reaction mechanisms

ASJC Scopus subject areas

  • Inorganic Chemistry

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