New methods of boron-oxygen bond formation in the decahydro-closo-decaborate(2-) anion have been worked out. The interaction between [closo-B10H10](2-) and ethers in the presence of CF3SO3H has been considered. The degree of substitution in boron clusters depends on the amount of triflic acid and the synthetic conditions. The compounds obtained were characterized by IR and NMR (H-1,B-11 and C-13) spectroscopy. The crystal structures of some mono- and disubstituted derivatives of the doso-decaborate anion were determined by X-ray diffraction. (C) 2015 Elsevier Ltd. All rights reserved.