Bis(oxazolinylmethyl)pyrrole derivatives and their coordination as chiral "pincer" ligands to rhodium.


Bis(oxazolinylmethyl)pyrrole derivatives (R)L(N)H (4a-e), which were designed as protioligands for meridionally coordinating "pincer" ligands, were synthesized by cyclization of pyrrole-2,5-diethylacetate with a series of chiral amino alcohols. Deprotonation of (R)L(N)H (4a-d) with tBuLi and subsequent reaction with [RhCl(CO)(2)](2) gave the corresponding rhodium(I) complexes [Rh((R)L(N))(CO)] (R = iPr: 5a, Ph: 5b, Bn: 5c, Ind: 5d), which were also prepared by reaction of (R)L(N)H with one molar equivalent of [Rh(acac)(CO)(2)]. Upon heating the compounds at 100 degrees C in toluene over a period of 2-5 h, complete rearrangement via a 1,3-H shift between the pyrrole ring and the bridging methylene groups took place to yield the corresponding isomeric complexes [Rh(iso-(R)L(N))(CO)] (6a-d). The transformation induced a planarization of the tridentate ligand system, resulting from the formation of a series of conjugated double bonds. Stirring the rhodium(I) complex 5a with an excess of CH(3)I in dichloromethane at ambient temperature(14) gave the octahedrally coordinated product of an oxidative addition [Rh((iPr)L(N))(CH(3))I(CO)] (7), while reaction of complex 5a with one molar equiv of CsBr(3) as a mild brominating reagent in toluene at 80 degrees C led to complete conversion of the rhodium(I) species to the dibromorhodium(III) complex [Rh(iso-(iPr)L(N))Br(2)(CO)] (8).

DOI: 10.1021/ic901189k

Cite this paper

@article{Konrad2009BisoxazolinylmethylpyrroleDA, title={Bis(oxazolinylmethyl)pyrrole derivatives and their coordination as chiral "pincer" ligands to rhodium.}, author={Felix Konrad and Julio Lloret Fillol and Hubert Wadepohl and Lutz H Gade}, journal={Inorganic chemistry}, year={2009}, volume={48 17}, pages={8523-35} }