Mixed complexes formed by lithioacetonitrile and chiral lithium amides: observation of (6)li,(15)N and (6)Li,(13)C couplings due to both C-Li and N-Li contacts

NMR spectroscopic studies have been performed on the mixed complexes formed by the lithium salt of acetonitrile (LiCH(2)CN) and the chiral lithium amides Li-(S)-N-(2-methoxybenzyl)-1-amino-1-phenyl-2-ethoxyethane (Li-1) and Li-(S)-N-isopropyl-2-amino-1-phenyl-3-methoxypropane (Li-2) in diethyl ether and tetrahydrofuran solvent. In diethyl ether Li-1 and LiCH(2)CN form a mixed dimeric (1:1) complex, while Li-2 and LiCH(2)CN form a mixed trimeric (2:1) complex. The dimer undergoes fast exchange between ketenimine and bridged structures. Both (1)J((15)N,(6)Li) and (1)J((13)C,(6)Li) couplings were observed for the respectively isotopically labeled compounds. In the trimeric complex the CH(2)CN anion also undergoes fast degenerate exchange between ketenimine and bridged structures, and the complex appears C(2)-symmetric on the NMR spectroscopy time scale. Both the dimer and trimer complexes have the bridged acetonitrile anion in common, as indicated by the highly shielded alpha-carbon (13)C NMR shifts (delta -6.1 and -7.4, respectively). In tetrahydrofuran only N-metalated mixed LiCH(2)CN dimers were observed for both Li-1 and Li-2 with the less shielded (13)C NMR shifts of delta -2.5 and -2.2 for the alpha-carbon of LiCH(2)CN of the complexes.