Computational NMR of the iron pyrazolylborate complexes [Tp₂Fe]⁺ and Tp₂Fe including solvation and spin-crossover effects

Transition metal complexes have important roles in many biological processes as well as applications in fields such as pharmacy, chemistry and materials science. Paramagnetic nuclear magnetic resonance (pNMR) is a valuable tool in understanding such molecules, and theoretical computations are often advantageous or even necessary in the assignment of experimental pNMR signals. We have employed density functional theory (DFT) and the domain-based local pair natural orbital coupled-cluster method with single and double excitations (DLPNO-CCSD), as well as a number of model improvements, to determine the critical hyperfine part of the chemical shifts of the iron pyrazolylborate complexes [Tp2Fe]+ and Tp2Fe using a modern version of the Kurland-McGarvey theory, which is based on parameterising the hyperfine, electronic Zeeman and zero-field splitting interactions via the parameters of the electron paramagnetic resonance Hamiltonian. In the doublet [Tp2Fe]+ system, the calculations suggest a re-assignment of the 13C signal shifts. Consideration of solvent via the conductor-like polarisable continuum model (C-PCM) versus explicit solvent molecules reveals C-PCM alone to be insufficient in capturing the most important solvation effects. Tp2Fe exhibits a spin-crossover effect between a high-spin quintet (S = 2) and a low-spin singlet (S = 0) state, and its recorded temperature dependence can only be reproduced theoretically by accounting for the thermal Boltzmann distribution of the open-shell excited state and the closed-shell ground-state occupations. In these two cases, DLPNO-CCSD is found, in calculating the hyperfine couplings, to be a viable alternative to DFT, the demonstrated shortcomings of which have been a significant issue in the development of computational pNMR.