Acyl chloride carbon insertion into dicarbaborane cages - new route to tricarbollide cages

0443636 - ÚACH 2016 RIV US eng J - Journal Article
Štíbr, Bohumil
Acyl chloride carbon insertion into dicarbaborane cages - new route to tricarbollide cages.
Pure and Applied Chemistry. Roč. 87, č. 2 (2015), s. 135-142. ISSN 0033-4545. E-ISSN 1365-3075.
[IMEBORON/15./. Praha, 24.08.2014-28.08.2014]
R&D Projects: GA ČR(CZ) GAP207/11/0705
Institutional support: RVO:61388980
Keywords : acyl chlorides * carbon insertion * carboranes * IMEBORON-XV * metallatricarbollides * tricarbollides
Subject RIV: CA - Inorganic Chemistry
Impact factor: 2.615, year: 2015

Reactions between the arachno-6,9-C2B8H14 dicarbaborane and acyl chlorides, RCOCl, in the presence of amine bases in CH2Cl2, followed by acidification with conc. H2SO4 at 0 degrees C, generate in high yields a series of neutral alkyl and aryl tricarbollides of structure 8-R-nido-7,8,9-C3B8H11 (where R = alkyls and aryls). These skeletal alkylcarbonation (SAC) reactions are consistent with an aldol-type condensation between the RCO group and open-face dicarbaborane hydrogen atoms, which is associated with the insertion of the acyl chloride RC unit into the structure under elimination of three extra hydrogen atoms as H2O and HCl. The reactions thus result in an effective cross-coupling between R and the tricarbollide cage. High-temperature reactions between 8-Ar-nido-7,8,9-C3B8H11 (where Ar = Ph, 1-C10H7, and 2-C10H7) compounds and [CpFe(CO)(2)](2) produced the first types of monoaryl substituted twelve-vertex ferratricarbollide complexes of general constitution [1-(CpFe)-closo-ArC3B8H10] with three different arrangements of cluster carbon vertexes. The Fe-complexation is accompanied by extensive rearrangement of the cluster carbon atoms over the twelve-vertex cage and the complexes isolated can be regarded as ferrocene analogues.
Permanent Link: http://hdl.handle.net/11104/0246363