Lewis pairing and frustration of group 13/15 elements geometrically enforced by (ace)naphthalene, biphenylene and (thio)xanthene backbones.
Chem Soc Rev
; 50(9): 5777-5805, 2021 May 07.
Article
em En
| MEDLINE
| ID: mdl-33972963
ABSTRACT
The synthesis, structure, and reactivity of mixed group 13/group 15 compounds (E13 = B, Al, Ga, In, Tl; E15 = N, P, Sb, Bi) featuring a rigid (ace)naphthalene or (thio)xanthene backbone are discussed in this review. The backbone may either enforce or prevent E15âE13 interactions, resulting in Lewis pairing or frustration. The formation of strong E15âE13 interactions is possible upon peri-substitution of (ace)naphthalenes. This gives the opportunity to access and study highly reactive species, as exemplified by P-stabilised borenium salts and boryl radicals. In turn, rigid expanded spacers such as biphenylenes, (thio)xanthenes and dibenzofurans impose long distances and geometrically prevent E15âE13 interactions. Such P-B derivatives display ambiphilic coordination properties and frustrated Lewis pair behaviour towards small molecules, their preorganised structure favouring reversible interaction/activation. Throughout the review, the importance of the scaffold in enforcing or preventing E15âE13 interactions is highlighted and discussed based on experimental data and theoretical calculations.
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MEDLINE
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En
Ano de publicação:
2021
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Article