The 1,1,3-tris(diisopropylamino)diphosphirenium salt 1 reacts with lithium aluminium hydride leading to the P-hydrogeno-C-phosphinophosphaalkenes 2, which on treatment with a catalytic amount of BF3·OEt2 afford the 1,3-bis(diisopropylamino)-1H-diphosphirene 3. The corresponding η1-coordinated 1H-diphosphirene 6 can be prepared by treatment of 2 or 3 with one equivalent of [W(CO)5(thf)]. Alternatively, the diphosphirenium salt 1 reacts with an excess of [W(CO)5(thf)], affording the corresponding η1-coordinated diphosphirenium salt complex 4, which is converted into the P-hydrogenophosphaalkene complex 5 with lithium aluminium hydride. The dinuclear tungsten complexes 7 and 8 are obtained by treatment of the free 1H-diphosphirene 3 with two equivalents of [W(CO)5(thf)] or one equivalent of [W(CO)4(thf)2], respectively. Compound 6 reacts with two equivalents of hydrogen chloride, giving the 1-chloro-3-diisopropylamino-1H-diphosphirene 9, which can be subsequently converted into the 1-diisopropylamino-, 1-azido, or 1-phenyl-3-diisopropylamino-1H-diphosphirenes 6, 10 and 11 by nucleophilic substitution with diisopropylamine, azidotrimethylsilane or sodium tetraphenylborate, respectively. The [η2-(3-diisopropylaminodiphosphirenylium salt)·W(CO)5] complexes 12a-c can be prepared by reaction of 9 with silver trifluoromethanesulfonate, aluminium or gallium trichloride or, alternatively, by treatment of 6 with two equivalents of trifluoromethanesulfonic acid. Reaction of 12a with diisopropylamine, water, bis(triphenylphosphoranylidene)ammonium chloride or tetrabutylammonium fluoride gives the corresponding 1H-diphosphirene complexes 6, 13, 9, or 14, respectively. Compound 12a also reacts with one or two equivalents of [W(CO)5(thf)], leading to the di- and tri-nuclear complexes 15and 16, respectively.