η5-Cyclopentadienylrhodium(I) complexes containing diphosphines and their reactions with the electrophiles H+ and Me+. Crystal and molecular structure of [Rh(η-C5H5)(CO)(Ph2PCH2PPh2)], a complex with a unidentate bis(diphenylphosphino)methane ligand

The compounds [Rh(η-C5H5)(dppm)(CO)] (2), [Rh(η-C5H5)(dppe)] (3), and [Rh(η-C5H5)(dppp)] (4) were obtained from the reactions of [Rh(η-C5H5)(CO)2] (1) with bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), and 1,3-bis(diphenylphosphino) propane (dppp) respectively. The X-ray structure determination of (2) shows it to crystallize in the space group P21/n with unit-cell dimensions a = 13.734(4), b = 9.771(3), c = 20.440(8) Å, β = 103.9(1)°, and Z = 4. R′ = 0.05 for 2 864 observed reflections. Some relevant bond distances are Rh-(centroid of C5H5 ring) = 1.932, Rh-P = 2.238(2), and Rh-C(carbonyl) = 1.806(8) Å. The bonding of the dppm ligand is, unusually, unidentate to the metal. The reactions of (2), (3), (4), and of the previously reported complex [{Rh(η-C5H5)(CO)}2(μ-dppb)] (6) [dppb = 1,4-bis(diphenylphosphino) butane], with the electrophilic agents H+ and Me+ have been studied. Complex (3) reacts with HBF4 to give the cationic hydride [Rh(η-C5H5)H(dppe)]BF4 (5); in the same reaction (4) and (6) gave unstable products. The protonic attack of HCl on (3), (4), and (6) results in the formation of compounds devoid of co-ordinated cyclopentadienyl ion. The binuclear complex [{Rh(CO)(μ-Cl)}2(μ-dppb)] (7) was the product of the reaction of (6) with HCl; for this reaction a possible mechanism is proposed. The reactions of HCl with (3) and (4) are more complex and mixtures containing [{Rh(P-P)Cl}n] and the rhodium(III) hydride [{RhH(P-P)Cl2}n] (n = 1 or 2, P-P = dppe or dppp) were isolated. The compound [{Rh(dppe)Cl}2] was formed by the reaction of (5) with [AsPh4]Cl. The electrophilic attack of Mel on (2) takes place either at the metal or at the unco-ordinated phosphorus atom of dppm and the reaction product is [Rh(η-C5H5)(COMe)I(Ph2PCH 2PMePh2)]I. Mel reacts with (3) and (4) to give [Rh(η-C5H5)Me(dppe)]I and [Rh(η-C5H5)Me(dppp)]I, which are very unstable in solution.