The boron analogues of homo- and hetero-alkyl substituted pyrophosphates, bis-(alkylphosphite)boranium tetrafluoroborates were synthesized by the reaction of trialkylphosphiteborane, triphenylcarbenium tetrafluoroborate and trialkylphosphite in yields ranging from 36 to 40%. All compounds were characterized by elemental analyses, H-1, B-11 and C-13 NMR and IR spectroscopy. (C) 2002 Elsevier Science B.V. All rights reserved.