Diorganophosphane oxides were employed as preligands for the synthesis of catalytically active transition metal complexes of the phosphinous acids (CF3)(2)POH and (C2F5)(2)POH. Their reactions with solid PtC12 and PdC12 led to the formation of mononuclear phosphinous acid complexes [Cl2M{P(Rf)(2)OH2] (M = Pd, Pt; Rf = C2F5, CF3), which can be crystallized, for example, as its pyridinium salts, 2[HPy][Cl2Pd{P(CF3)(2)O}(2)](2-). In vacuo HCl is liberated from the neutral palladium complexes affording mixtures of di- and polynudear complexes. Moreover, (C2F5)(2)POH was reacted with several fidiketonato complexes of palladium, platinum, and nickel yielding air- and moisture-stable complexes [(acac)M{[P(Rf)(2)O](2)H}], featuring a quasichelating phosphinous acid phosphinito unit {P(R-f)(2)O center dot center dot center dot H center dot center dot center dot O(Rf)(2)Pr. Treatment of [Ni(Cp)(2)] (Cp = cyclopentadienyl) and [(cod)RhC112 (cod = 1,5-cyclooctadiene) with (C2F5)(2)POH leads to the substitution of one Cp or chloro ligand by a quasichelating unit. The novel coordination compounds were characterized by NMR and IR spectroscopies, mass spectrometry, and X-ray diffraction analysis. The platinum complex [(acac)Pti[P(C2F5)(2)O](2)H-1] (acac = acetylacetonato) was used for the construction of hetero-bimetallic complexes by the treatment with [(cod)RhCl](2) and [Ni(Cp)(2)]. The trinudear bimetallic complex [{(acac)Pt[P(C2F5)20]2}2Ni] is the first structurally characterized hetero-bimetallic species containing a bis(perfluoroalkyOphosphinito bridge.