Selection of a Pentameric Host in the Host–Guest Complexes {[{[P(μ‐N<i>t</i>Bu)]₂(μ‐NH)}₅]⋅I}⁻[Li(thf)₄]⁺ and [{[P(μ‐N<i>t</i>Bu)]₂(μ‐NH)}₅]⋅HBr⋅THF

Abstract

The structures of the host-guest complexes [[[[P(mu-NtBu)]2(mu-NH)]5]I]-.[Li(thf)4]+ [2.I[Li(thf)4]] and [[[P(mu-NtBu)]2(mu-NH)]5].HBr.THF (2.HBr.THF) show that increased distortion of the framework of the pentameric macrocycle [[[P(mu-NtBu)]2(mu-NH)]5] (2) occurs with the larger halide ions. Theoretical studies show that the thermodynamic stabilities of the model host-guest anions [2.X]- (X=Cl, Br, I) are in the order Cl- approximately Br->I-, that is, the reverse of the templating trend observed experimentally. These studies support the view that the selection of the pentamer 2 over the tetramer [[[P(mu-NtBu)]2(mu-NH)]4] (1) is kinetically controlled, a conclusion which is also consistent with the previous observation that the frameworks of 1 and 2 are not in dynamic equilibrium with each other.