Crystal and molecular structures of the nido-carborane anions, 7,9- and 2,9 C₂B₉H₁₂

Fox, M.A.; Goeta, A.E.; Hughes, A.K.; Johnson, A.L.

Abstract

Deboronation of meta-carborane, closo-1,7-C2B10H12, with refluxing piperidine results in the quantitative formation of [(C5H10NH)(2)H+](nido-7,9-C2B9H12-) whose structure was determined by X-ray diffraction. Heating under vacuum liberates piperidine to give (C5H10NH2+)(nido-7,9-C2B9H12-). The reaction of meta-carborane with KOH in refluxing ethanol yields K+ nido-7,9-C2B9H12- and the cage substituted anion 10-EtO-7,9-C2B9H11-. The protonated Proton Sponge salt (PSH+)(nido-7,9-C2B9H12-) (PS=1,8-N,N,N',N'-tetramethylnaphthalenediamine) was obtained by metathesis from the potassium salt, an X-ray crystallographic study located the bridging hydrogen in the anion on the open face between the two adjacent boron atoms. Anaerobic deboronation of para-carborane, closo-1,12-C2B10H12, with KOH in refluxing tetraglyme-toluene gives the potassium salt of nido-2,9-C2B9H12- from which 2,9-C2B9H13 was isolated in 45% yield by protonation. The salt (PSH+)(nido-2,9-C2B9H12-), obtained from nido-2,9-C2B9H13 and PS, was shown by single crystal X-ray crystallography to contain a hydrogen bridging two boron atoms opposite the carbon atom on the open face. Aerobic deboronation of para-carborane with KOH forms closo-1,10-C2B8H10 and 2-HO-closo-1,10-C2B8H9 in low yields. Fully assigned multinuclear NMR (B-11,C-13 and H-1) data are reported for the isomeric 7,8-, 7,9- and 2,9-nido-C2B9H12- anions and neutral 7,8- and 2,9-C2B9H13, and compared with computed shifts (at the GIAO B3LYP/6-311G* level) from optimized (at MP2/6-31G*) geometries.

Citation

Fox, M., Goeta, A., Hughes, A., & Johnson, A. (2002). Crystal and molecular structures of the nido-carborane anions, 7,9- and 2,9 C₂B₉H₁₂. Dalton Transactions, 10, 2132-2141. https://doi.org/10.1039/b108937d

• Journal Article Type: Article
• Publication Date: 2002-03
• Deposit Date: Apr 12, 2007
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 10
• Pages: 2132-2141
• DOI: https://doi.org/10.1039/b108937d
• Public URL: https://durham-repository.worktribe.com/output/1594447