Abstract: Tetracyclic tetraamino phosphoranes of the formula ##EQU1## wherein X is F, C.sub.6 H.sub.5, or C.sub.1 -C.sub.6 alkyl, and tricyclic polyamino phosphine oxides of the formula ##EQU2## wherein x and y are each 2 or 3 Z is --(CH.sub.2)-- where z is 2 to 10 and x + y + z is 7 to 14 orZ is --(CH.sub.2)--NH--(CH.sub.2)-- where v and w are each 2 or 3Are prepared by reacting a silylated cyclic polyamine of the formula ##EQU3## wherein Q is --(CH.sub.2)-- or ##EQU4## with a fluorophosphorane of the formulaXPF.sub.4orPOF.sub.3,provided that when Q is --(CH.sub.2)--, the fluorophosphorane is POF.sub.3. The corresponding alkoxy or amino [X=OR, NR.sub.2 or N(CH.sub.2).sub.2.sub.-6, where R is C.sub.1 -C.sub.6 alkyl] tetracyclic tetraaminophosphoranes are obtained by reaction of an alkali metal alkoxide or amide with the tetracyclic fluorophosphorane. The methyl iodide salts of the tetracyclic tetraamino phosphoranes are also described.