Temperature-dependent anionic phospho-Fries rearrangements of ferrocenyl/phenyl phosphates P(O)(OFc)(n)(OPh)(3) (- n), (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4); n = 0,1,2,3) were investigated. Whereas ferrocenyls solely undergo one rearrangement per reaction step, the number of phenyl-based 1,3-O -> C shifts depends on the temperature. This results in different types of otherwise hardly accessible mixed ferrocenyl/phenyl organophosphorus compounds. Detailed investigations of the triple-rearrangement of triphenyl phosphate (n = 0) reveals a consecutive formation of its phosphonate and phosphinate prior to the known phosphane oxide. (C) 2016 Elsevier B.V. All rights reserved.