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A novel redox reaction involving fluoride and phosphine complexes of palladium(I1) is reported. The scope of this reaction has been investigated using the ligands PPh3, Ph2P(CH2),PPh2 (n = 1-4), Ph2PCH,C(CH3),CH2PPh2, Ph2PCHS, and P(CH2CH,CN),; several solvents including DMSO, pyridine, acetonitrile, and THF; and either n-BuJF.3H20 or KF/ 18-crown-6 as the fluoride source. The reduction groducts are palladium(0) phosphine complexes for which this reaction offera a convenient synthetic route. 'P and lgF NMR spectra permitted identification of the initial oxidation products as difluorophosphoranes (R3PF2), which subsequently hydrolyzed, forming phosphine oxides if a hydrated fluoride source is used. Results implicating a fluoride-induced redox reaction in the thermal decomposition ofare also presented. Preliminary results indicate that platinum complexes also undergo this reaction, but nickel complexes yield NiF2. The X-ray parameters for Pd(dppp), dppp 13.290 (1) a c = 20.186 (2) 1, B = 109.383 (5)O, and 2 = 4. = 1,3-bis(di henyphosphino) ropane) are: monoclinic, space group C2/c (No. 15), a = 18.396 (2) s , b =

Reaction of tri(3-methylindolyl)methane (1) with PCl3 in the presence of triethylamine produces the bicyclic π-acid phosphatri(3-methylindolyl)methane (2). The unconstrained analogue tri(N-3-methylindolyl)phosphine (3) was synthesized by reaction of lithium 3-methylindolide with PCl3. Both 2 and 3 are stable to hydrolysis, alcoholysis, and aerial oxidation. Reactions of 2 with tBuOOH, S8, or Se powder under forcing conditions produce the chalcogenide derivatives 2O (4), 2S (5), and 2Se (6), respectively. Tri(N-3-methylindolyl)phosphine selenide (7) and SeP(N-pyrrolyl)3 (8) were synthesized by reaction of Se powder with 3 and P(N-pyrrolyl)3, respectively. The reaction of 2 with Rh(acac)(CO)2 (acac = acetylacetonate) under forcing conditions yields Rh(acac)(CO)(2) (9), whereas Rh(acac)(CO)(3) (10) was synthesized by reaction of 3 with Rh(acac)(CO)2 under mild conditions. Spectroscopic data for 6−10 were used to assess the electronic properties of 2 and 3. Reduced σ-basicity of 2 and 3 is indicated by lack of their reactivity with methyl iodide. Furthermore, comparison of the 1 J P - Se values of 6−8 shows the parent phosphines to be slightly stronger σ-bases than P(OPh)3, but much weaker than triaminophosphines. In addition, comparison of the νCO data of 9 and 10 with those of known Rh(acac)(CO)(PR3) complexes shows 2 is a stronger π-acid than P(N-pyrrolyl)3 and P(OPh)3, while 3 has π-acceptor properties similar to P(OPh)3. The molecular structures of compounds 2, 4, and 9 were determined by X-ray crystallography.