Quantitative and chemically intuitive evaluation of the nature of M-L bonds in paramagnetic compounds: application of EDA-NOCV theory to spin crossover complexes

Chemistry : a European Journal
Sally BrookerFederico Totti

Abstract

With the aim of improving understanding of M-L bonds in 3d transition metal complexes, quantitative analysis by Energy Decomposition Analysis and Natural Orbital for Chemical Valence model (EDA-NOCV) is done on octahedral spin crossover (SCO) complexes, as the transition temperature (T1/2) is sensitive to subtle changes in M-L bonding. EDA-NOCV analysis of Fe-N bonds in 5 [FeII( Lazine )2(NCBH3)2], in both low spin (LS) and paramagnetic high spin (HS) states, led to (a) development of a general, widely applicable, corrected M+L6 fragmentation, tested against a family of 5 LS [FeII( Lazine )3(BF4)2], confirming that 3 Lazine are stronger ligands (ΔEorb,σ+π ≈ -370 kcal/mol) than 2 Lazine + 2 NCBH3 (≈ -335 kcal/mol), as observed; (b) analysis of Fe-L bonding on LS → HS, reveals more ionic (ΔEelstat) and less covalent (ΔEorb) character (ΔEelstat:ΔEorb 55:45 LS → 64:36 HS), mostly due to a big drop in σ- (ΔEorb,σ ↓50%; -310 → -145 kcal/mol), and a drop in π- contributions (ΔEorb,π ↓90%; -30 → -3 kcal/mol); (c) strong correlation of observed T1/2 and ΔEorb,σ+π, for both LS and HS families (R2 =0.99 LS, R2 = 0.95 HS), but no correlation of T1/2 and ΔΔEorb,σ+π(LS-HS) (R2 =0.11). Overall, this study has established and validated a gener...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Apr 5, 2002·Chemistry : a European Journal·R SieberA Hauser
May 22, 2003·Journal of Computational Chemistry·E Van Lenthe, E J Baerends
Feb 11, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Keisaku NakanoSumio Kaizaki
Apr 25, 2006·Physical Chemistry Chemical Physics : PCCP·Florian Weigend
Oct 7, 2006·Journal of Molecular Modeling·Mariusz Mitoraj, Artur Michalak
Feb 13, 2008·The Journal of Physical Chemistry. a·Artur MichalakTom Ziegler
Feb 19, 2008·Journal of Molecular Modeling·Mariusz Mitoraj, Artur Michalak
Jun 24, 2010·Journal of the American Chemical Society·Kengo OkaYuichi Shimakawa
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Mar 30, 2011·Journal of Molecular Modeling·Mariusz Paweł MitorajArtur Michalak
May 17, 2014·The Journal of Chemical Physics·Andrii RudavskyiRia Broer
Apr 14, 2009·Journal of Chemical Theory and Computation·Mariusz P MitorajTom Ziegler
Feb 26, 2016·Inorganic Chemistry·Kasper P Kepp
Nov 29, 2016·Physical Chemistry Chemical Physics : PCCP·Walter A Rabanal-LeónRamiro Arratia-Pérez
Jan 4, 2017·Journal of the American Chemical Society·Michael J MurphySuzanne M Neville
Apr 14, 2017·Journal of the American Chemical Society·Hoa PhanMichael Shatruk
Nov 8, 2017·Inorganic Chemistry·Santiago Rodríguez-Jiménez, Sally Brooker
Nov 22, 2017·Journal of the American Chemical Society·Santiago Rodríguez-JiménezSally Brooker
Oct 27, 2018·Journal of Computational Chemistry·Paul JerabekGernot Frenking
Dec 15, 2018·Chemistry, an Asian Journal·Santiago Rodríguez-JiménezSally Brooker
Jan 4, 2019·Nature Communications·Maksim KunitskiReinhard Dörner
Feb 16, 2019·Chemical Reviews·Kristian E DalleErwin Reisner
Jun 30, 2019·Chemical Reviews·Lili ZhaoGernot Frenking
Sep 21, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Tim StauchMartin Head-Gordon
Dec 10, 2019·Angewandte Chemie·Wenlong YangRobert J Gilliard
Feb 6, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Nis-Julian H KneuselsIstemi Kuzu
Mar 20, 2020·Chemistry : a European Journal·Guohai DengGernot Frenking

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Citations

Sep 24, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Peter M ChappleYann Sarazin

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Software Mentioned

ORCA
EDA
ALMO
ADF
NOCV
natural orbital for chemical valence theory ( NOCV )

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