Double Friedel-Crafts acylation reactions on the same ring of a metallocene: synthesis of a 2,5-diacetylphospharuthenocene.

The synthetic outcome of the Friedel-Crafts acylation of 1',2',3,3',4,4',5'-heptamethylphospharuthenocene reflects the nature of the acylating agent, with alkanoyl anhydride/trifluoromethanesulfonic acid (TfOH) reagents giving monosubstitution at the phospholyl ring, whereas alkanoyl chloride/AlCl(3) gives 2,5-disubstitution. DFT calculations indicate that this unusual double acylation can be facilitated by the intervention of the phosphorus atom at an early stage in the reaction trajectory, with the acyl group being delivered from the phosphorus atom into the ring 2- or 2,5-positions.

A comparison of phosphaferrocene and phospharuthenocene ligands in Rh+-catalysed enamide hydrogenation reactions: superior performance of the phospharuthenocene.

Enantiopure Cp*-substituted 3,4-dimethyl-5-phenylphosphametallocene-2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH(2)PPh(2) phosphametallocenes (13: M=Fe; 14: M=Ru) and 2-CH(2)PtBuR substituted phospharuthenocenes (R=tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(eta(2)-L)](+)BF(4)(-) (L=13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.

Synthesis, structure and dynamics of methoxynaphthalene-substituted phospha-ruthenocenes and -ferrocenes.

The syntheses of potassium 2-(2'-methoxynaphth-1'-yl)-3,4-dimethyl-5-phenylphospholide 4 and eta5-pentamethylcyclopentadienyl(eta5-2-(2-methoxynaphth-1-yl)-3,4-dimethyl-5-phenylphospholyl)-ruthenium(II)5 and -iron(II)6 are described. The barrier to rotation of the naphthyl group (79 kJ mol-1 and 72 kJ mol-1 in CD2Cl2 respectively) characterises 5 and 6 as potential tropos type ligands. Coordination of 5 to [PtCl2(PEt3)] gives two cis and two trans complexes [PtCl2(PEt3)5] wherein rotation about the phospholyl-naphthyl vector is slow.

Synthesis and resolution of the planar chirality of ester-functionalised phospharuthenocenes.

Menthyl phospholide ester anions provide an operationally simple and high yielding entry to the first planar chiral enantiopure phospharuthenocene derivatives.

Synthesis of 2-silyl substituted phospharuthenocenes and an elaboration into the first phospharuthenocene-phosphine.

A [1,5] shift protocol transiently hindering the 2-position of phospholide anions provides an access to sterically unencumbered phospharuthenocenes and the first phospharuthenocene-phosphine.