Year: 2026
Type: preprint
Abstract: The first examples of air stable acyclic triorganoiodine compounds, phenyliodine bis(1-(2-R)-o-carborane)s have been isolated from reactions of PhIL2 reagents with lithio-o-carboranes and crystallographically characterized. When R = H or Si(CH3)3, the complexes are predisposed to form o-carboryne through β-elimination as confirmed by a trapping reaction with naphthalene, where the R = H variant degrades during formation. The latter Si(CH3)3 derivative is isolable in modest yield, while for R = CH3, the resulting phenyliodine bis(1-(2-methyl)-o-carborane)s can be obtained in high yields. The complexes known so far appear to behave as nonnucleophilic bases, and treatment with strong protic acids affords more electrophilic phenyl(1-o-carboranyl) iodonium salts. Compared with our previous synthesis of an aryl(1-o-carboranyl) iodonium salt, this method is simpler and offers broadened scope. Less is known of these salts than previously assumed as earlier reports have now also been found incorrect. A preliminary study finds they can either arylate or 1-o-carboranylate a chloride nucleophile with chemoselectivity tuneable by electronic modification of the oCb ligand, providing a rare example of an o-carborane C atom reacting as an electrophile.
Source: ChemRxiv
Institutions: La Trobe University, Monash University
Language: English
Topic: Boron Compounds in Chemistry
Subfield: Radiology, Nuclear Medicine and Imaging
Field: Medicine
Domain: Health Sciences
Open Access status: green
OpenAlex ID: W7221983651