To improve understanding of M-L bonds in 3d transition metal complexes, analysis by energy decomposition analysis and natural orbital for chemical valence model (EDA-NOCV) is desirable as it provides a full, quantitative and chemically intuitive ab initio description of the M-L interactions. In this study, a generally applicable fragmentation and computational protocol was established and validated by using octahedral spin crossover (SCO) complexes, as the transition temperature (T1/2 ) is sensitive to subtle changes in M-L bonding. Specifically, EDA-NOCV analysis of Fe-N bonds in five [FeII (Lazine )2 (NCBH3 )2 ], in both low-spin (LS) and paramagnetic high-spin (HS) states led to: 1) development of a general, widely applicable, corrected M+L6 fragmentation, tested against a family of five LS [FeII (Lazine )3 ](BF4 )2 complexes; this confirmed that three Lazine are stronger ligands (ΔEorb,σ+π =-370 kcal mol-1 ) than 2 Lazine +2 NCBH3 (=-335 kcal mol-1 ), as observed. 2) 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-1 ), and a drop in π contributions (ΔEorb,π ↓90 %; -30→-3 kcal mol-1 ). 3) 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 an EDA-NOCV protocol for M-L bonding analysis of any diamagnetic or paramagnetic, homoleptic or heteroleptic, octahedral transition metal complex. This new and widely applicable EDA-NOCV protocol holds great promise as a predictive tool.
Keywords: M−L bonding; paramagnetism; spin crossover; theoretical chemistry.
© 2020 The Authors. Published by Wiley-VCH GmbH.