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

摘要

The complex [Rh(kappa(3)-N,N,N-pybox)(CO)][PF6] (1) has been prepared reaction of the precursor [Rh(mu-Cl)(eta(2)-C2H4)(2)](2), 2,6-bis[4'(S)isopropyloxazolin-2'-yl]pyridine (pybox), CO, and NaPF6. Complex 1 reacts with monodentate phosphines to give the complexes [Rh(kappa(1)-N-pybox)(CO)(PR3)(2)][PF6] (R-3 = MePh2 (2), Me2Ph (3), (C3H5)Ph-2 (4)), which show a previously unseen monodentate coordination of pybox. Complex 1 undergoes oxidative addition reactions with iodine and CH3I leading to the complexes [RhI(R)(kappa(3)-N,N,N-pybox)(CO)][PF6] (R = I (5); R = CH3 (6)). Furthermore, a new allenyl Rh(III)-pybox complex of formula [Rh(CH=C=CH2)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. [References: 17]