A study of the Group 1 metal tetra-aza macrocyclic complexes [M(Me4cyclen)(L)]+ using electronic structure calculations

Abstract

Metal-cyclen complexes have a number of important applications. However, the coordination chemistry between metal ions and cyclen-based macrocycles is much less well studied compared to their metal ion-crown ether analogues. This work, which makes a contribution to address this imbalance by studying complex ions of the type [M(Me₄cyclen)(L)]⁺, was initiated by results of an experimental study which prepared some Group 1 metal cyclen complexes, namely [Li(Me₄cyclen)(H₂O)][BAr^F] and [Na(Me₄cyclen)(THF)][BAr^F] and obtained their X-ray crystal structures [J. M. Dyke, W. Levason, M. E. Light, D. Pugh, G. Reid, H. Bhakhoa, P. Ramasami, and L. Rhyman, Dalton Trans., 2015, 44, 13853]. The lowest [M(Me₄cyclen)(L)]⁺ minimum energy structures (M = Li, Na, K, and L = H₂O, THF, DEE, MeOH, DCM) are studied using density functional theory (DFT) calculations. The geometry of each [M(Me₄cyclen)(L)]⁺ structure and, in particular, the conformation of L are found to be mainly governed by steric hindrance which decreases as the size of the ionic radius increases from Li⁺ → Na⁺ → K⁺. Good agreement of computed geometrical parameters of [Li(Me₄cyclen)(H₂O)]⁺ and [Na(Me₄cyclen)(THF)]⁺ with the corresponding geometrical parameters derived from the crystal structures [Li(Me₄cyclen)(H₂O)]⁺[BAr^F]⁻ and [Na(Me₄cyclen)(THF)]⁺[BAr^F]⁻ is obtained. Bonding analysis indicates that the stability of the [M(Me₄cyclen)(L)]⁺ structures originates mainly from ionic interaction between the Me₄cyclen/L ligands and the M⁺ centres. The experimental observation that [M(Me₄cyclen)(L)]⁺[BAr^F]⁻ complexes could be prepared in crystalline form for M⁺ = Li⁺ and Na⁺, but that experiments aimed at synthesising the corresponding K⁺, Rb⁺, and Cs⁺ complexes failed resulting in formation of [Me₄cyclenH][BAr^F] is investigated using DFT and explicitly correlated calculations, and explained by considering production of [Me₄cyclenH]⁺ by a hydrolysis reaction, involving traces of water, which competes with [M(Me₄cyclen)(L)]⁺ formation. [Me₄cyclenH]⁺ formation dominates for M⁺ = K⁺, Rb⁺, and Cs⁺ whereas formation of [M(Me₄cyclen)(L)]⁺ is energetically favoured for M⁺ = Li⁺ and Na⁺. The results indicate that the number and type of ligands, play a key role in stabilising the [M(Me₄cyclen)]⁺ complexes and it is hoped that this work will encourage experimentalists to prepare and characterise other [M(Me₄cyclen)(L)]⁺ complexes.