Chemistry of the Heterotriquinanes and Heterotriquinacenes

Abstract

Triquinanes are tricyclic hydrocarbons that have fused cyclopentane rings. Although there are linear and angular triquinanes that are doubly fused, this Account focuses exclusively on the ‘triquinacane’, or triply fused structure with a heteroatom (nitrogen or oxygen) on the C _3v symmetry axis. Azatriquinane- and oxatriquinane-based species tend to show remarkable and often unexpected chemistry, and have variously comprised the most basic trialkyl amine, a superbasic proton chelate, trigonal pyramidal ligand platforms, novel calixiform hosts, aromatic hemispheres of hetero-C₂₀ fullerenes, cocrystallizing agents for eliminating rotational disorder in fullerene crystals, the first water-stable, chromatographable trialkyloxonium species, the first isolable allylic oxonium species, world-record C–O bond lengths, rapid S_N2 reaction at a tertiary center, and R₄O²⁺ (oxadionium) species.

1 Introduction

2 Azatriquinane

3 Azatriquinacene

4 Aromatic Azatriquinacene-Based Systems

5 Oxatriquinane

6 Tetravalent Oxygen

7 Oxatriquinacene

8 The Future

Key words

aromaticity - hemifullerenes - hypervalency - molecular curvature - oxonium ions - triquinanes - triquinacenes

Publication History

Received: 03 September 2021

Accepted after revision: 22 September 2021

Article published online:
29 October 2021

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