Synthesis and structure of tris(alkyl- and silyl-tetramethylcyclopentadienyl) complexes of lanthanum

In efforts to make sterically crowded tris(peralkylcyclopentadienyl) complexes of lanthanum for the exploration of sterically induced reduction chemistry with a diamagnetic system, the synthesis of (C(5)Me(4)R)(3)La complexes has been pursued with R = Me, Et, (i)Pr, and SiMe(3). The complexes were synthesized in four steps: reaction of LaCl(3) with KC(5)Me(4)R to form (C(5)Me(4)R)(2)LaCl(2)K(THF)(2), addition of allylmagnesium chloride to make (C(5)Me(4)R)(2)La(C(3)H(5)), protonolysis with Et(3)NHBPh(4) to make [(C(5)Me(4)R)(2)La][BPh(4)], and finally the replacement of BPh(4)(-) with C(5)Me(4)R(-) using KC(5)Me(4)R to make (C(5)Me(4)R)(3)La. X-ray crystallographic data were obtainable on the (C(5)Me(4)R)(3)La complexes for R = Me, Et, (i)Pr, and SiMe(3). In each complex, the three C(5)Me(4)R ring centroids define a trigonal planar geometry around La. The average La-(ring centroid) distances are 2.64, 2.65, 2.66, and 2.69 A for the Me, Et, (i)Pr, and SiMe(3) structures, respectively, with La-C distances ranging from 2.857 (3) to 3.029 (2) A. Despite the steric crowding, ligand exchange can be observed by NMR spectroscopy.