SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF NITROGEN BASE ADDUCTS OF DECAMETHYLSAMAROCENE - (C5ME5)2SM(NH2CME3) AND (C5ME5)2SM(N-MEIM)2

(C5Me5)2Sm(THF)2 and (C5Me5)2Sm(THF) do not react with Me3CNH2 in THF, toluene or hexanes, but (C5Me5)2Sm reacts in toluene to form hexane soluble (C5Me5)2Sm(NH2CMe3) (1) in high yield. Compound 1 crystallizes from benzene with benzene in the lattice as (C5Me5)2Sm(NH2CMe3).(C6 H6)0.5 in the monoclinic space group P2(1)/c(C2h(5); No. 14) with unit cell parameters at 173 K of a = 17.036(3) angstrom, b = 21.538(4) angstrom, c = 14.441(2) angstrom, beta = 91.814(12)-degrees, V = 5296.1(15) angstrom3 and D(calcd) = 1.34 g cm-3 for Z = 8. Least squares refinement of the model based on 5480 reflections (\F-degrees\ > 3.0 sigma(\F-degrees\)) converged to a final R(F) = 5.0%. In the two independent molecules in the unit cell, the Me3CNH2 groups are attached to the bent metallocenes with 2.804(10) angstrom and 2.737(7) angstrom Sm-N distances and 112.2(5)-degrees Sm-N-C angles. The average Sm-C(C5Me5) distance is 2.816(16) angstrom and the (ring centroid)-Sm-(ring centroid) angles are 142.1-degrees and 140.4-degrees. (C5Me5)2Sm(THF)2 reacts with 2 equiv. of N-methylimidazole (N-MeIm) in THF to form THF soluble (C5Me5)2Sm(N-MeIm)2 (2) in quantitative yield. Compound 2 crystallizes from THF in the monoclinic space group P2(1)/c(C2h(5); No. 14) with unit cell parameters at 163 K of a = 16.059(7) angstrom, b = 10.291(4) angstrom, c = 17.635(5) angstrom, beta = 101.00(3)-degrees, V = 2861(2) angstrom3 and D(calcd) = 1.36 g cm-3 for Z = 4. Least squares refinement of the model based on 2824 reflections (\F-degrees\ > 4.0sigma(\F-degrees\)) converged to a final R(F-degrees) = 5.9%. the N-MeIm ligands are attached to the bent metallocene with Sm-N distances of 2.618(10) angstrom and 2.673(10) angstrom. The N-Sm-N angle is 84.2(3)-degrees and the centroid-Sm-centroid angle is 138.0-degrees. The average Sm-C(C5Me5) distance is 2.853(10) angstrom.