Rhodium(I) and Rhodium(III) complexes containing the chiral ligand 2,6-bis[4'(S)-isopropyloxazolin-2'-yl]pyridine (pybox): an unprecedented monohapto coordination of pybox

The complex Rh(kappa(3)-N,N,N-pybox)(CO)]PF(6)] (1) has been prepared by reaction of the precursor Rh(mu-Cl)(eta(2)-C(2)H(4))(2)](2), 2,6-bis4'(S)-isopropyloxazolin-2'-yl]pyridine (pybox), CO, and NaPF(6). Complex 1 reacts with monodentate phosphines to give the complexes Rh(kappa(1)-N-pybox)(CO)(PR(3))(2)]PF(6)] (R(3) = MePh(2) (2), Me(2)Ph (3), (C(3)H(5))Ph(2) (4)), which show a previously unseen monodentate coordination of pybox. Complex 1 undergoes oxidative addition reactions with iodine and CH(3)I leading to the complexes RhI(R)(kappa(3)-N,N,N-pybox)(CO)]PF(6)] (R = I (5); R = CH(3) (6)). Furthermore, a new allenyl Rh(III)-pybox complex of formula Rh(CH=C=CH(2))Cl(2)(kappa(3)-N,N,N-pybox)] (7) has been synthesized by a one-pot reaction from Rh(mu-Cl)(eta(2)-C(2)H(4))(2)](2), pybox, and an equimolar amount of propargyl chloride.