Models contend iodine double bonds


I-O bonds within the periodate ion are usually represented as double bonds (left), but AdNDP suggests they are dative (right) © Wiley-VCH

Hypervalent iodine reagents are widely used in organic synthesis, but their structures haven’t been studied in detail. In the majority of textbooks and papers, they are drawn with double bonds between iodine and oxygen, nitrogen or carbon.

But a new study has used theoretical models to show that this might be incorrect. Instead, it suggests the bonds within some of these compounds are dative, with iodine donating the electron pair.

A team led by Alexander Boldyrev and Viktor Zhdankin at Utah State University in the US examined the nature of the bonds within compounds such as iodosylbenzene (PhIO) and the periodate ion (IO4-) using a bond modelling technique called adaptive natural density partitioning (AdNDP). Their calculations revealed the bonds to be dative rather than double.

The group says the discovery will be useful when it comes to understanding reaction mechanisms, and suggests the textbooks may need correcting.

References

A S Ivanov et al, Angew. Chem. Int. Ed., 2014, DOI: 10.1002/anie.201405142


Related Content

What is a bond?

30 January 2014 Premium contentFeature

news image

There’s more to bonding than covalent, ionic and the lines we draw between atoms on paper. Philip Ball takes on the expandi...

‘Tetrel bonding’ emerges from σ-hole

11 October 2013 Research

news image

Non-covalent bonds between electron donors and silicon, tin or germanium are strong but overlooked

Most Read

No-frills coats set a trend for designer viruses

26 August 2014 Research

news image

An artificial protein that self-assembles around and protects DNA could be ideal for gene therapy, nanomachines and synthetic...

Rigid molecular wires make electrons fly

29 August 2014 Research

news image

Organic wires conduct electrons 800 times faster than other molecular counterparts by letting them hitch a ride on a vibratio...

Most Commented

Rigid molecular wires make electrons fly

29 August 2014 Research

news image

Organic wires conduct electrons 800 times faster than other molecular counterparts by letting them hitch a ride on a vibratio...

Concerns over chemical treatment of reclaimed fracking fluid

29 August 2014 Research

news image

Current recycling procedure may do more harm than good