Dioxaphosphabicyclooctanes: small caged phosphines from tris(hydroxymethyl)phosphine

Dioxaphosphabicyclo[2.2.2]octanes (L1-L4) have been prepared in a one-pot reaction from tris(hydroxymethyl)phosphine and various alpha,beta-unsaturated ketones. The non-volatile phosphines oxidise very slowly in air. They possess highly upfield 31P chemical shifts (-59 to -70 ppm), small cone angles (121-140 degrees) and a similar electronic parameter to PPh3. Reaction of L1 with [Rh(acac)(CO)2] gave the complex [Rh(acac)(CO)(L1)] with a nu(C0000000000000000000000000000000000000000000000000000111111111111111000000000000000000011111111111111100000000000000000001111111111111110000000000000000000000000000000000000000000000000000O) of 1981.5 cm-1, whereas reaction L1 with [Rh(CO)2Cl]2 gave [Rh(CO)(L1)2Cl] with a nu(CO) of 1979.9 cm-1, remarkably similar to the CO stretching frequencies reported for analogous PPh3 complexes. The cage phosphines were explored as ligands in rhodium catalysed hydroformylation of 1-octene. All of the ligands gave a linear selectivity to n-nonanal of 68%, regardless of the substituents. However the ligand substituents had a significant effect on the catalyst activity, with increased steric bulk around the coordination environment giving a three-fold increase in aldehyde yield. The phosphines undergo ligand subsitution with [Pd(MeCN)2Cl2] forming square planar trans-[Pd(L)2Cl2] complexes. Subsequent reduction with hydrazine furnishes homoleptic tetravalent [Pd(L1)4] which was applied as a catalyst in Suzuki-Miyaura couplings, furnishing the C-C coupled products in moderate yields. The synthesis and coordination chemistry of sterically small caged phosphines, and their applications as ligands in homogeneous catalysis.