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This review highlights a number of synthetic applications of low-coordinate main group molecules generated in situ under mild conditions; so called “masked species”. Examples of masked monomeric and dimeric species from groups 13 to 15 are presented, as well as one noteworthy example from group 12. Finally, some masked heteroatomic E–E′ bonds are discussed. The utility of this class of compounds towards analysis of the reactivity of low-coordinate main group species; the formation of main group multiple bonds; the synthesis transition metal complexes of otherwise unstable main group species; the in situ formation of unusual elemental allotropes under ambient conditions and as materials precursors are emphasised.

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