Halogen bond shortens and strengthens the bridge bond of 1.1.1]propellane and the open form of 2.2.2]propellane

Joy, Jyothish and Akhil, Edakkandy and Jemmis, Eluvathingal D (2018) Halogen bond shortens and strengthens the bridge bond of 1.1.1]propellane and the open form of 2.2.2]propellane. In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 20 (40). pp. 25792-25798.

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Abstract

Detailed electronic structural analysis of 1.1.1]propellane and the open form of 2.2.2]propellane, especially their highest occupied molecular orbital (HOMO), shows the existence of significant electronic congestion at their bridge bond. The HOMO of 1.1.1]propellane is a spread-out orbital of its inverted tetrahedral bridgehead atoms. The HOMO of the open form of 2.2.2]propellane is an anti-bonding combination of its bridgehead atoms due to the stabilizing through-bond interaction. This unique spatial disposition of the HOMO enables a high electron density at the bridgehead atoms. Herein, we utilize the electron scavenging power of halogen bond donors to extract a fraction of destabilizing electrons from the bridge bond with the aim to alleviate its electronic congestion, which results in shortening and strengthening of the bridge bond with a reduction in the bond order. This result answers the seminal question raised by K. B. Wiberg in 1983, how can one have a relatively strong bond' without much bonding character?

Item Type:	Journal Article
Publication:	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Publisher:	ROYAL SOC CHEMISTRY
Additional Information:	Copy right for this article belong to ROYAL SOC CHEMISTRY
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	13 Nov 2018 15:25
Last Modified:	13 Nov 2018 15:25
URI:	http://eprints.iisc.ac.in/id/eprint/61036

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